CN101157544A - Perovskite oxide, process for producing the perovskite oxide, piezoelectric body, piezoelectric device, and liquid discharge device - Google Patents
Perovskite oxide, process for producing the perovskite oxide, piezoelectric body, piezoelectric device, and liquid discharge device Download PDFInfo
- Publication number
- CN101157544A CN101157544A CNA2007101542712A CN200710154271A CN101157544A CN 101157544 A CN101157544 A CN 101157544A CN A2007101542712 A CNA2007101542712 A CN A2007101542712A CN 200710154271 A CN200710154271 A CN 200710154271A CN 101157544 A CN101157544 A CN 101157544A
- Authority
- CN
- China
- Prior art keywords
- phase
- piezoelectrics
- crystalline
- electric field
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000007788 liquid Substances 0.000 title claims description 61
- 230000008569 process Effects 0.000 title abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 134
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 230000005684 electric field Effects 0.000 claims description 162
- 239000013078 crystal Substances 0.000 claims description 72
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 54
- 230000010287 polarization Effects 0.000 claims description 49
- 238000002441 X-ray diffraction Methods 0.000 claims description 47
- 230000002269 spontaneous effect Effects 0.000 claims description 44
- 239000000758 substrate Substances 0.000 claims description 41
- 229910052726 zirconium Inorganic materials 0.000 claims description 25
- 230000004304 visual acuity Effects 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 230000005621 ferroelectricity Effects 0.000 claims description 20
- 229910052697 platinum Inorganic materials 0.000 claims description 20
- 229910052758 niobium Inorganic materials 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 16
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910052712 strontium Inorganic materials 0.000 claims description 11
- 229910052741 iridium Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052702 rhenium Inorganic materials 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 101100215617 Arabidopsis thaliana ADO3 gene Proteins 0.000 abstract description 6
- 230000009466 transformation Effects 0.000 description 118
- 150000002500 ions Chemical class 0.000 description 36
- 239000010936 titanium Substances 0.000 description 36
- 239000000976 ink Substances 0.000 description 35
- 238000013461 design Methods 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 31
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 29
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 28
- 239000000463 material Substances 0.000 description 28
- 229910052719 titanium Inorganic materials 0.000 description 22
- 239000010955 niobium Substances 0.000 description 21
- 238000006073 displacement reaction Methods 0.000 description 20
- 230000000694 effects Effects 0.000 description 19
- 238000005516 engineering process Methods 0.000 description 15
- 238000007639 printing Methods 0.000 description 14
- 230000007704 transition Effects 0.000 description 12
- 230000001939 inductive effect Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 229910003460 diamond Inorganic materials 0.000 description 9
- 239000010432 diamond Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000005381 potential energy Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 229910052706 scandium Inorganic materials 0.000 description 5
- 229910020684 PbZr Inorganic materials 0.000 description 4
- 229910003077 Ti−O Inorganic materials 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000002075 main ingredient Substances 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910004121 SrRuO Inorganic materials 0.000 description 2
- 229910007746 Zr—O Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 241000877463 Lanio Species 0.000 description 1
- 229910020018 Nb Zr Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 210000002659 acromion Anatomy 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- -1 oxonium ion Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003362 replicative effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/14—Structure thereof only for on-demand ink jet heads
- B41J2/14201—Structure of print heads with piezoelectric elements
- B41J2/14233—Structure of print heads with piezoelectric elements of film type, deformed by bending and disposed on a diaphragm
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
- C04B35/2683—Other ferrites containing alkaline earth metals or lead
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
- C04B35/457—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates based on tin oxides or stannates
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
- H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
- H10N30/076—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by vapour phase deposition
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/093—Forming inorganic materials
- H10N30/097—Forming inorganic materials by sintering
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/704—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive films or coatings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8536—Alkaline earth metal based oxides, e.g. barium titanates
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8548—Lead-based oxides
- H10N30/8554—Lead-zirconium titanate [PZT] based
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8561—Bismuth-based oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
- C04B2235/3234—Titanates, not containing zirconia
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3296—Lead oxides, plumbates or oxide forming salts thereof, e.g. silver plumbate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/762—Cubic symmetry, e.g. beta-SiC
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/768—Perovskite structure ABO3
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Particle Formation And Scattering Control In Inkjet Printers (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A process for producing a piezoelectric oxide having a composition (A, B, C) (D, E, F)O3, where each of A, B, C, D, E, and F represents one or more metal elements. The composition is determined so as to satisfy the conditions (1), (2), (3), and (4), <in-line-formulae description=''In-line Formulae'' end=''lead''>0.98<=TF(P)<=1.01, (1) <in-line-formulae description=''In-line Formulae'' end=''tail''> <in-line-formulae description=''In-line Formulae'' end=''lead''>TF(ADO3)>1.0, (2) <in-line-formulae description=''In-line Formulae'' end=''tail''> <in-line-formulae description=''In-line Formulae'' end=''lead''>TF(BEO3)<1.0, and (3) <in-line-formulae description=''In-line Formulae'' end=''tail''> <in-line-formulae description=''In-line Formulae'' end=''lead''>TF(BEO3)<TF(CFO3)<TF(ADO3), (4) <in-line-formulae description=''In-line Formulae'' end=''tail''> where TF(P) is the tolerance factor of the perovskite oxide, and TF(ADO3), TF(BEO3), and TF(CFO3) are respectively the tolerance factors of the compounds ADO3, BEO3, and CFO3.
Description
Technical field
The present invention relates to perofskite type oxide, be used to prepare the method for this perofskite type oxide, contain this perofskite type oxide ferroelectricity mixture, piezoelectrics, use the piezo-electric device of these piezoelectrics and use the liquid discharge device of these piezoelectrics.
Background technology
At present, for example adopt the piezo-electric device that constitutes by piezoelectrics and electrode as the actuator that is installed on the ink jet print head.In this piezo-electric device, according to the increase of the strength of electric field that is imposed on piezoelectrics by electrode with pre-determined direction with reduce, these piezoelectrics expand and shrink.For example, perofskite type oxide such as PZT (lead zirconate titanate) are the known materials that is applicable to piezoelectrics.Even such material is the ferroelectric substance that also shows spontaneous polarization when not applying electric field.According to reports, this piezoelectric the morphotropy phase boundary (morphotropic phase boundary, MPB) and near show high piezoelectric property.
PZT is PbTiO
3(PT) and PbZrO
3(PZ) sosoloid.Figure 14 be PZT with respect to temperature and titanium molar fraction (that is PbTiO, in PZT
3Molar fraction) phasor.The phasor of Figure 14 is quoted in following document: " Landolt-Bornstein:Numerical Data and FunctionalRelationships in Science and Technology; New Series; " Group III:Crystal andSolid State Physics, 16 volumes, edit Springer-Verlag Berlin-Heidelberg-New York (1981) 426) ﹠amp by K.H.Hellwege and A.M.Hellwege; Figure 72 8.In Figure 14, FT represents tetragonal phase, and FR represents the rhombus crystalline phase.
When Ti forms when high, PZT trends towards forming quadratic crystal, and forms when high as Zr, trends towards forming rhomboidan.When the mole of Ti and Zr is formed approaching equating, obtain MPB and form.For example, the mol ratio of preferred zirconium and titanium is 52/48, and this mol ratio approaches MPB and forms.About the instruction of the textbook of piezoceramic material, near MPB and MPB, become instability and piezoelectric property of crystalline structure becomes the highest.Normally, PZT forms false cubic system near MPB and MPB according to reports.Yet the details of the nanostructure of PZT is not also known.
In these cases, Japanese unexamined patent publication 2006-036578 report, the PZT-base ceramic material is such as Pb (Ti, Zr, Nb) O
3Sintered compact near MPB and MPB, formed the two-phase mixed crystal (referring to, for example, the claim 9 among the Japanese unexamined patent publication 2006-036578) of quadratic crystal and rhomboidan.In addition, Japanese unexamined patent publication 2006-036578 disclose can design ideally based on the relation between the phase fraction of piezo-electric modulus and pros and rhombus crystalline phase composition (referring to, for example, the table 1 among the Japanese unexamined patent publication 2006-036578, Fig. 4 and 0027 section).
In addition, following document has also been reported the PZT film and has been formed by the two-phase mixed crystal of quadratic crystal and rhomboidan near MPB and MPB: S.Yokoyama etc. " CompositionalDependence of Electrical Properties of Highly (100)-/(001)-Oriented Pb (Zr, Ti) O
3Thick Films Prepared on Si Substrates by Metalorganic Chemical VaporDeposition "; Japanese Journal of Applied Physics; 42 volumes; 5922-5926 page or leaf; 2003 (referring to; for example, Fig. 2 in the Yokoyama reference paper (b)).
Yet, in the conventional piezo-electric device of the first kind, by direction electric field is imposed on ferroelectrics usually, to utilize the expansible piezoelectric activity of ferroelectrics on the spontaneous polarization direction along spontaneous polarization.That is, thought that conventionally it is important being designed to piezoelectric along applying electric field on the spontaneous polarization direction.Yet, only to utilize under the situation of the expansible piezoelectric activity on the spontaneous polarization direction, the amount of displacement (displacement) is restricted, but the bigger displacement of current needs.
Japanese Patent 3568107 has proposed the conventional piezo-electric device of second class, and wherein the application of electric field has been induced in the intravital phase transformation of piezoelectricity.Japanese Patent 3568107 discloses a kind of piezo-electric device that is made of phase-change film, electrode and heating member, and in this device, heating member connects the temperature regulation of phase-change film the degree (referring to, the claim 1 in the Japanese Patent 3568107) of nearly Curie temperature Tc.Japanese Patent 3568107 mention use a kind of at the film that takes place between tetragonal phase and the rhombus crystalline phase or between cube crystalline phase and pros or rhombus crystalline phase to change as phase-change film (referring to, the claim 2 in the Japanese Patent 3568107).In addition, Japanese Patent 3568107 reports, the piezo-electric device of the disclosed second class routine can obtain bigger displacement than the conventional piezo-electric device of the first kind in this Japanese Patent 3568107, and reason is that the piezoelectric activity of this ferroelectric substance and the changes of crystal relevant with phase transformation all help this displacement.
As mentioned above, although according to common report, PZT forms false cubic system near MPB and MPB, but Japanese unexamined patent publication 2006-036578 and Yokoyama reported in literature the PZT-base ceramic material near MPB and MPB, form the two-phase mixed-crystal structure that contains tetragonal phase and rhombus crystalline phase.Yet, aspect the piezoelectricity mechanism of MPB and MPB vicinity and crystalline structure many, remain unknown.
In addition, according to disclosed technology in Japanese unexamined patent publication 2006-036578, must carry out following operation: a plurality of samples that prepare the perofskite type oxide that each free multiple predetermined-element with different molar fractions constitutes; Analyze by X-ray diffraction and Rietveld, obtain the tetragonal phase in each sample and the phase fraction of rhombus crystalline phase; Obtain the piezo-electric modulus in each sample; And based on the definite composition of the relation between phase fraction that is obtained and the piezo-electric modulus.Yet, according to above-mentioned technology, when the formation element of sample changes, all must look for required composition, thereby the material design can not be carried out efficiently by this technology by experimentizing.
Incidentally, as mentioned above, Japanese Patent 3568107 proposed to adopt between tetragonal spheroidal and the rhombohedral system or the film that between isometric system and pros or rhombohedral system, undergoes phase transition as phase-change film.Yet disclosed piezo-electric device is that supposition is used in Curie temperature Tc vicinity in Japanese Patent 3568107.Because Curie temperature Tc is corresponding to the transformation temperature between ferroelectric phase and paraelectric phase, therefore when film used near Curie temperature Tc, film all was not created in the phase transformation between tetragonal phase and the rhombus crystalline phase.That is, disclosed piezo-electric device can not utilize other phase transformation the phase transformation between ferroelectric phase and paraelectric phase in Japanese Patent 3568107.In addition, owing to do not produce spontaneous polarization in para-electric, therefore disclosed piezo-electric device does not show the expansible piezoelectric activity on direction of polarization that the response electric field applies after phase transformation in Japanese Patent 3568107.
The inventor and the colleague who belongs to this transferee have proposed to use so a kind of piezoelectrics in piezo-electric device in Japanese unexamined patent publication 2007-116091 (requiring the benefit of priority of Japanese patent application 2005-277108 formerly), and these piezoelectrics contain the zone with crystalline orientation in first ferroelectric phase.In these piezoelectrics, when when piezoelectrics apply electric field, first ferroelectric phase from corresponding to first crystallographic system of at least a portion in the aforementioned region changes second ferroelectric phase corresponding to second crystallographic system that is different from first crystallographic system into.
In above-mentioned piezo-electric device, can realize by with the volume change that causes from the relevant changes of crystal of the phase transformation of first ferroelectric phase.In addition, owing to all produce piezoelectric activity in the two at first ferroelectric phase (before the phase transformation) and second ferroelectric phase (after the phase transformation), therefore when when piezoelectrics apply electric field, disclosed piezo-electric device shows bigger displacement than disclosed piezo-electric device in Japanese Patent 3568107 in Japanese unexamined patent publication 2007-116091.
In addition, Japanese unexamined patent publication 2007-116091 has reported, electric field is different from the phase transformation orientation of the spontaneous polarization axle in ferroelectric phase before along its direction that imposes on piezoelectrics, and during the preferred approximate orientation that is same as the spontaneous polarization axle in ferroelectric phase after the phase transformation, the structural domain effect of design (engineered-domain effect) etc. has increased deflection (displacement).
Summary of the invention
The present invention finishes in view of such circumstances.
First purpose of the present invention provides a kind of method for preparing perofskite type oxide based on the novel material principle of design, this novel material principle of design is to have excellent piezoelectric property (promptly for design, ferroelectric properties) perofskite type oxide proposes, wherein this method is particularly suitable for preparing the perofskite type oxide that uses in the piezo-electric device that proposes in Japanese unexamined patent publication 2007-116091, and this piezo-electric device utilization applies the inductive phase transformation of electric field institute.
Second purpose of the present invention provides a kind of perofskite type oxide by method for preparing.
The 3rd purpose of the present invention provides a kind of ferroelectricity mixture and piezoelectrics that contain by the perofskite type oxide of method for preparing.
The 4th purpose of the present invention provides piezo-electric device and the liquid discharge device that uses above-mentioned piezoelectrics.
(I) in order to realize above-mentioned first purpose, according to a first aspect of the invention, provide a kind of method that is used to prepare perofskite type oxide.In addition, in order to realize above-mentioned second purpose, according to a second aspect of the invention, provide perofskite type oxide by described according to a first aspect of the invention method preparation.This perofskite type oxide had by forming that following composition formula is represented:
(A，B，C)(D，E，F)O
3， (P)
In the formula, each among A, B, C, D, E and the F is all represented one or more metallic elements, and A, B and C represent A-bit element, and D, E and F represent the beta-position element, and O represents oxygen element.A-bit plain A, B can be different with C, perhaps two kinds among A-bit element A, B and the C or all can be identical.Yet when two kinds among A-bit plain A, B and the C or whole when identical, beta-position element D, E are different with F.In addition, beta-position element D, E and F can be different, perhaps two kinds among beta-position element D, E and the F or all can be identical.Yet when two kinds among beta-position element D, E and the F or whole when identical, plain A, B are different with C for the A-bit.Although the integral molar quantity of A-bit element and the integral molar quantity of beta-position element are generally 1: 3 with respect to the ratio of the molar weight of Sauerstoffatom separately, by composition formula (A, B, C) (D, E, F) O
3The composition of expression can form in the scope of perovskite structure, and the integral molar quantity of A-bit element and the integral molar quantity of beta-position element can depart from 1: 3 with respect to the ratio of the molar weight of Sauerstoffatom separately.Method feature according to first aspect present invention is, determines mixture (A, B, C) (D, E, F) O
3Composition, to satisfy the condition of inequality (1) to (4) expression.
0.98≤TF(P)≤1.01 (1)
TF(ADO
3)＞1.0 (2)
TF(BEO
3)＜1.0 (3)
TF(BEO
3)＜TF(CFO
3)＜TF(ADO
3)。(4)
In this manual, TF (X) is the tolerance factor of the oxide compound represented by composition formula X, but perofskite type oxide (A, B, C) (D, E, F) O
3Tolerance factor be expressed as TF (P).Described tolerance factor is defined as
TF＝(rA+rO)/√2(rB+rO)，
In the formula, rA is the average ion radius of A-bit element, and rB is the average ion radius of beta-position element, and rO is the ionic radius of oxonium ion.In this manual, ionic radius is the Shannon ionic radius.(referring to, R.D.Shannon, " Revised effective ionic radii and systematicstudies of interatomic distances in halides and chalcogenides ", ActaCrystallographica, A32 (1976), the 751-767 page or leaf.) the average ion radius is represented that by ∑ CiRi in the formula, Ci represents the molar fraction of each ion in lattice site, and Ri is the ionic ionic radius.
According to a first aspect of the invention, obtain oxide compound (A, B, C) (D, E, F) O in theory
3, ADO
3, BEO
3And CFO
3In each tolerance factor, and determine perofskite type oxide (A, B, C) (D, E, F) O like that by above-mentioned
3Composition.At this moment, even one or more in the oxide compound self do not form perovskite structure by them, also can obtain each the tolerance factor in the oxide compound in theory.
Preferably, perofskite type oxide can be by the method preparation according to first aspect present invention, make this perofskite type oxide also have a kind of or arbitrarily possible combination of following supplementary features (i) in (iv), and can also comprise a kind of or arbitrarily possible combination of following supplementary features (i) in (iv) according to the perofskite type oxide of second aspect present invention.
(i) preferably, determine perofskite type oxide (A, B, C) (D, E, F) O
3Composition, further to satisfy condition by inequality (5) expression.That is, preferably, further satisfy condition by inequality (5) expression according to the composition of the perofskite type oxide of second aspect present invention.
0.98≤TF(CFO
3)≤1.02 (5)
(ii) the phase structure of perofskite type oxide has no particular limits.For example, perofskite type oxide can have wherein three component ADO
3, BEO
3And CFO
3The three-phase mixed-crystal structure of coexistence, perhaps three component ADO wherein
3, BEO
3And CFO
3Solid solution becomes monophasic phase structure fully.In addition, perofskite type oxide can have other structure.
(iii) preferably, the perofskite type oxide according to second aspect present invention comprises the first component ADO
3, the second B component EO
3With the 3rd component CFO
3At the first component ADO
3, the second B component EO
3With the 3rd component CFO
3In each component in, the molar weight of A-bit element and the molar weight of beta-position element are generally 1: 3 with respect to the ratio of the molar weight of Sauerstoffatom separately, however at the first component ADO
3, the second B component EO
3With the 3rd component CFO
3Can form separately in the scope of perovskite structure, the molar weight of A-bit element and the molar weight of beta-position element can depart from 1: 3 with respect to the ratio of the molar weight of Sauerstoffatom separately.
(iv) in having feature perofskite type oxide (iii), further preferably, the first component ADO
3With the second B component EO
3Form respectively corresponding to the structure of the isomorphous system not, and particularly preferably be the first component ADO
3, the second B component EO
3With the 3rd component CFO
3Form respectively corresponding to the structure of the isomorphous system not.
For example, perofskite type oxide can have the three-phase mixed-crystal structure, wherein said first component forms corresponding to the first a kind of crystalline structure in square, oblique side, monocline, three parts and the rhombohedral system, second component forms and to be different from first crystalline structure and corresponding to square, the oblique second a kind of crystalline structure in side and the rhombohedral system, and the 3rd component form corresponding to cube and false isometric system in the 3rd a kind of crystalline structure.
Example according to the perofskite type oxide of second aspect present invention had by forming that following composition formula is represented,
Pb(Ti，Zr，M)O
3， (PX)
In the formula, at mixture Pb (Ti, Zr, M) O
3In M be at least a among metallic element Sn, Nb, Ta, Mo, W, Ir, Os, Pd, Pt, Re, Mn, Co, Ni, V and the Fe.
Another kind of example according to the perofskite type oxide of second aspect present invention had by forming that following composition formula is represented,
(Ba，Ca，Sr)(Ti，Zr，M)O
3， (PY)
In the formula, at mixture (Ba, Ca, Sr) (Ti, Zr, M) O
3In M be at least a among metallic element Sn, Nb, Ta, Mo, W, Ir, Os, Pd, Pt, Re, Mn, Co, Ni, V and the Fe.
Another kind of example according to the perofskite type oxide of second aspect present invention had by forming that following composition formula is represented,
Bi(Al，Fe，M)O
3， (PW)
In the formula, at mixture Bi (Al, Fe, M) O
3In M be at least a among metallic element Cr, Mn, Co, Ni, Ga and the Sc.
(II) in addition, in order to realize above-mentioned second purpose, also provide perofskite type oxide according to third aspect present invention.Be characterised in that to have according to the piezoelectrics of third aspect present invention and locate or near it composition in morphotropy phase boundary (MPB), and has a mixed-crystal structure that constitutes by at least two first crystalline phases and at least one second crystalline phase, described first crystalline phase is square, oblique a kind of in side and the rhombus crystalline phase, and described second crystalline phase is cube and false cube crystalline phase at least a.
In addition, in order to finish above-mentioned second purpose, also provide perofskite type oxide according to fourth aspect present invention.Be characterised in that to have according to the piezoelectrics of fourth aspect present invention and locate or near it composition in morphotropy phase boundary (MPB), and in height explanation X-ray diffractogram, show tetragonal phase first diffraction peak, rhombus crystalline phase second diffraction peak and be different from tetragonal phase and the 3rd diffraction peak of the third phase of rhombus crystalline phase.
In this manual, near wording " at MPB or the it " meaning be the composition of perofskite type oxide when when this perofskite type oxide applies electric field, the taking place in the compositing range of transformation mutually of perofskite type oxide.
(III) in order to realize above-mentioned the 3rd purpose, provide ferroelectricity mixture according to fifth aspect present invention.Be characterised in that according to the ferroelectricity mixture of fifth aspect present invention and comprise according to of the present invention second the perofskite type oxide to one of fourth aspect.
In addition, in order to realize above-mentioned the 3rd purpose, also provide piezoelectrics according to sixth aspect present invention.Be characterised in that according to the piezoelectrics of sixth aspect present invention and comprise second the perofskite type oxide to one of fourth aspect according to the present invention.Piezoelectrics can be the piezoelectric film or the sintered compacies of for example piezoceramic material.
Preferably, the above-mentioned piezoelectrics according to sixth aspect present invention can comprise also that following supplementary features are (v) to (a kind of or possible combination arbitrarily viii).
(v) preferably, the piezoelectrics according to sixth aspect present invention comprise the ferroelectric phase with crystalline orientation.In this manual, the wording meaning that " has crystalline orientation " is that the orientation degree F by the Lotgerling commercial measurement is 80% or higher.This orientation degree is defined as
F(％)＝(P-P0)/(1-P0)×100，
In the formula, P be from total XRD (X-ray diffraction) intensity of oriented surface with respect to ratio from total XRD intensity of all crystal faces, and P0 is the value of P under the situation of sample completely random orientation.Under the situation of (001) orientation, P=∑ I (001)/∑ I (hkl), I in the formula (hkl) is the XRD intensity from crystal face (hkl), and ∑ I (001) is the total XRD intensity from crystal face (001), and ∑ I (hkl) is the total XRD intensity from all crystal faces (hkl).For example, under the situation of (001) orientation in the perovskite typed crystal, P=I (001)/{ I (001)+I (100)+I (101)+I (110)+I (111) }.When the sample completely random is orientated, F=0%.When sample is orientated fully, F=100%.
(vi) preferably, the piezoelectrics according to sixth aspect present invention comprise the zone in ferroelectric phase (ferroelectric domain) of crystalline orientation along the direction that is different from spontaneous polarization axle orientation.
(vii) has feature (under the situation vi) at piezoelectrics according to sixth aspect present invention, further preferably, ferroelectric phase is a kind of in the following crystalline phase: have approximate rhombus crystalline phase along＜100〉direction crystalline orientation, rhombus crystalline phase with the crystalline orientation on approximate edge＜110〉direction, tetragonal phase with the crystalline orientation on approximate edge＜110〉direction, tetragonal phase with the crystalline orientation on approximate edge＜111〉direction, have the iris phase of the crystalline orientation that is similar to edge＜100〉direction and iris phase with the crystalline orientation on approximate edge＜111〉direction.In this manual, the wording crystalline orientation of direction " have approximate edge＜abc〉" to look like be edge＜abc the orientation degree F of direction is 80% or higher.
(viii) has feature (vi) or (under the situation vii) at piezoelectrics according to sixth aspect present invention, further preferably, when electric field was imposed on piezoelectrics according to sixth aspect present invention along the direction that is different from spontaneous polarization axle orientation, at least a portion that is included in the above-mentioned ferroelectric phase in these piezoelectrics changed.
(IV) in order to realize above-mentioned the 4th purpose, provide piezo-electric device according to seventh aspect present invention.Piezo-electric device according to seventh aspect present invention is characterised in that piezoelectrics and the electrode that comprises according to sixth aspect present invention, by described electrode electric field is imposed on this piezoelectrics.
In addition, in order to realize above-mentioned the 4th purpose, also provide liquid discharge device according to eighth aspect present invention.Liquid discharge device according to eighth aspect present invention is characterised in that piezo-electric device, substrate and the discharge member that comprises according to seventh aspect present invention.This piezo-electric device is placed on the substrate.Discharge member is with the whole formation of substrate or separate formation, and comprises liquid storage chamber and liquid discharge outlet, and the liquid of wherein liquid storage chamber deposit liquid, and deposit in the liquid storage chamber is discharged by the liquid discharge outlet is external.
(V) the present invention has following advantage.
(a) a first aspect of the present invention provides a kind of novel material principle of design that preparation has the perofskite type oxide of excellent piezoelectricity (ferroelectric) performance that is used for.Therefore, according to a first aspect of the invention, can easily design the composition of perofskite type oxide with excellent piezoelectricity (ferroelectric) performance.
(b) the material principle of design that provides of first aspect present invention is suitable for designing the composition of the perofskite type oxide that uses in the system that proposes in Japanese unexamined patent publication 2007-116091, and this system uses the inductive phase transformation of electric field institute.According to the present invention, can provide a kind of perofskite type oxide, even, also be easy to generate phase transformation and produce big distortion (displacement) when when the strength of electric field that this perofskite type oxide applied is hanged down with such structural domain structure.
(c) by using perofskite type oxide, can provide a kind of piezo-electric device with excellent piezoelectric property according to material principle of design preparation provided by the invention.
Description of drawings
The tolerance factor TF of the various perofskite type oxides that Fig. 1 explanation ionic radius plain with the A-bit and the beta-position element is relevant and the figure of crystallographic system.
Fig. 2 schematically illustrates to be made of first ferroelectric phase fully and as the figure of the piezoelectric property of the piezoelectrics that are transformed into second ferroelectric phase when it applies electric field, wherein said first and second ferroelectric phases are corresponding to different crystallographic systems.
Fig. 3 A, 3B and 3C are the figure of example of the structural domain of the three kind crystallographic systems of explanation in phase transformation pattern 1, and described phase transformation pattern 1 is used for explaining that perofskite type oxide according to the present invention is in the validity of using by the system that applies electric field-induced phase transition.
Fig. 4 A is the figure that schematically illustrates potential energy and concern the distance from the center to the beta-position element in the structure cell of rhomboidan.
Fig. 4 B be schematically illustrate potential energy and cube or the structure cell of false cubic system in the figure that concerns the distance from the center to the beta-position element.
Fig. 5 A, 5B and 5C are the figure of example of the structural domain of the three kind crystallographic systems of explanation in phase transformation pattern 2, and described phase transformation pattern 2 is used for explaining that perofskite type oxide according to the present invention is in the validity of using by the system that applies electric field-induced phase transition.
Fig. 6 is the cross-sectional view that schematically illustrates the necessary cross section partly of the ink jet print head with piezo-electric device (as liquid discharge device) according to an embodiment of the invention.
Fig. 7 is the synoptic diagram of example of ink-jet recording device with ink jet print head of Fig. 6.
Fig. 8 is the top view of a part of the ink-jet recording device of Fig. 7.
Fig. 9 A is high resolving power XRD (X-ray diffraction) figure of piezoelectrics in specific embodiment 1.
Fig. 9 B is the height explanation XRD figure of the piezoelectrics in comparative example 1.
Figure 10 A to 10D is the figure of the EXAFS (expansion X-gamma absorption fine structure) of the piezoelectrics of explanation in specific embodiment 1 and comparative example 1.
Figure 11 is the figure of the high resolving power XRD figure of the piezoelectrics of explanation in the specific embodiment 2 that in various degree strength of electric field obtains.
Figure 12 is the figure of the high resolving power XRD figure of the piezoelectrics of explanation in specific embodiment 3.
Figure 13 A is the figure of the XRD figure of the piezoelectrics of explanation in specific embodiment 4.
Figure 13 B is near the enlarged view of a part of XRD figure of Figure 13 A of explanation diffraction angle (2 θ) is 46 degree.
Figure 14 is the phasor of PZT.
Embodiment
With reference to the accompanying drawings, describe a preferred embodiment of the present invention in detail.
1. perofskite type oxide
As illustrated in " summary of the invention ", a first aspect of the present invention provides a kind of method that is used to prepare the perofskite type oxide of being represented by following composition formula,
(A，B，C)(D，E，F)O
3， (P)
In the formula, each among A, B, C, D, E and the F is all represented one or more metallic elements, and A, B and C represent A-bit element, and D, E and F represent the beta-position element, and O represents oxygen element.A-bit plain A, B can be different with C, perhaps two kinds among A-bit element A, B and the C or all can be identical.Yet when two kinds among A-bit plain A, B and the C or whole when identical, beta-position element D, E are different with F.In addition, beta-position element D, E and F can be different, perhaps two kinds among beta-position element D, E and the F or all can be identical.Yet when two kinds among beta-position element D, E and the F or whole when identical, plain A, B are different with C for the A-bit.Although the integral molar quantity of A-bit element and the integral molar quantity of beta-position element are generally 1: 3 with respect to the ratio of the molar weight of Sauerstoffatom separately, by composition formula (A, B, C) (D, E, F) O
3The composition of expression can form in the scope of perovskite structure, and the integral molar quantity of A-bit element and the integral molar quantity of beta-position element can depart from 1: 3 with respect to the ratio of the molar weight of yyz separately.
The method that is used to prepare perofskite type oxide according to first aspect present invention is characterised in that, determines perofskite type oxide (A, B, C) (D, E, F) O
3Composition, to satisfy condition by inequality (1) to (4) expression.
0.98≤TF(P)≤1.01 (1)
TF(ADO
3)＞1.0 (2)
TF(BEO
3)＜1.0 (3)
TF(BEO
3)＜TF(CFO
3)＜TF(ADO
3)。(4)
Preferably, determine this perofskite type oxide (A, B, C) (D, E, F) O
3Composition, further to satisfy condition by inequality (5) expression.
0.98≤TF(CFO
3)≤1.02 (5)
In (5), TF (X) is the tolerance factor of the oxide compound represented by composition formula X at above-mentioned inequality (1), but perofskite type oxide (A, B, C) (D, E, F) O
3Tolerance factor be represented as TF (P).
In addition, as described at " summary of the invention ", a second aspect of the present invention provides by according to the prepared above-mentioned perofskite type oxide of the method for first aspect present invention.That is, the perofskite type oxide according to second aspect present invention has by above-mentioned composition formula (A, B, C) (D, E, F) O
3The composition of expression, and be characterised in that this perofskite type oxide (A, B, C) (D, E, F) O according to the perofskite type oxide of second aspect present invention
3Composition satisfy condition by above-mentioned inequality (1) to (4) expression.Preferably, perofskite type oxide (A, B, C) (D, E, F) O
3Composition satisfy condition by above-mentioned inequality (5) expression.
Whole when identical in beta-position element D, E and F, can be with composition formula (A, B, C) (D, E, F) O
3Be expressed as
(A，B，C)DO
3， (P1)
In the formula, each among A, B, C and the D is all represented one or more metallic elements, and A, B and C represent A-bit element, and D represents one or more beta-position elements, and O represents oxygen element, and A-bit plain A, B are different with C.
In this case, preferably, perofskite type oxide (A, B, C) DO
3Satisfy condition, and particularly preferably be perofskite type oxide (A, B, C) DO by following inequality (1a) to (4a) expression
3Further satisfy condition by following inequality (5a) expression.
0.98≤TF(P1)≤ 1.01 (1a)
TF(ADO
3)＞1.0 (2a)
TF(BDO
3)＜1.0 (3a)
TF(BDO
3)＜TF(CDO
3)＜TF(ADO
3) (4a)
0.98≤TF(CDO
3)≤ 1.02 (5a)
At inequality (1a), perofskite type oxide (A, B, C) DO
3Tolerance factor be represented as TF (P1).
In addition, in A-bit plain A, B and C under all identical situations, can be with composition formula (A, B, C) (D, E, F) O
3Be expressed as
A(D，E，F)O
3， (P2)
In the formula, each among A, D, E and the F is all represented one or more metallic elements, and A represents one or more A-bit elements, and D, E and F represent the beta-position element, and O represents oxygen element, and beta-position element D, E are different with F.
In this case, preferably, perofskite type oxide A (D, E, F) O
3Satisfy condition, and particularly preferably be perofskite type oxide A (D, E, F) O by following inequality (1b) to (4b) expression
3Further satisfy condition by following inequality (5b) expression.
0.98≤TF(P2)≤1.01 (1b)
TF(ADO
3)＞1.0 (2b)
TF(AEO
3)＜1.0 (3b)
TF(AEO
3)＜TF(AFO
3)＜TF(ADO
3) (4b)
0.98≤TF(AFO
3)≤1.02 (5b)
In inequality (1b), perofskite type oxide A (D, E, F) O
3Tolerance factor be represented as TF (P2).
Fig. 1 is the tolerance factor TF of the relevant various perofskite type oxides of explanation average ion radius plain with the A-bit and the beta-position element and the figure of crystallographic system, wherein have the ion of one or both elements on the A position in this perofskite type oxide, and on the B position of this perofskite type oxide, have the ion of one or both elements.
In Fig. 1, C represents cubic system, and M represents monoclinic crystal, and PC represents false cubic system, and R represents rhomboidan, and T represents quadratic crystal, and Tr represents three square crystals.In addition, the ionic radius of various elements is to show in conjunction with the symbol that respective element is used.Particularly, the ionic radius " 0.67 (dust) " that in Fig. 1, has shown trivalent Mn ionic ionic radius " 0.64 (dust) " and divalent manganesetion.
When tolerance factor TF equaled 1.0, the lattice of perovskite structure had the closest packing structure.Because under this condition, the beta-position ion moves in lattice hardly, so perofskite type oxide may have stable structure.When perofskite type oxide has this composition of realizing above-mentioned condition, this perofskite type oxide may have crystalline structure such as cube or false cubic crystal structure, and do not show ferroelectricity, or show low-down ferroelectricity.
When tolerance factor TF greater than 1.0 the time, the beta-position ion is less than A-position ion.Under this condition, even when lattice deformability, the beta-position ion also may carry out this lattice, and may move in this lattice.When perofskite type oxide had this composition of realizing above-mentioned condition, this perofskite type oxide may have crystalline structure such as quadratic crystal (wherein, the spontaneous polarization axle is along＜001〉direction orientation), and shows ferroelectricity.The trend that exists is that when the difference of tolerance factor and 1.0 increased, it is higher that ferroelectricity becomes.
When tolerance factor TF less than 1.0 the time, the beta-position ion is greater than A-position ion.Under this condition, the beta-position ion does not enter in the lattice, unless lattice deformability.When perofskite type oxide has this composition of realizing above-mentioned condition, this perofskite type oxide may have crystalline structure such as rhomboidal crystal (wherein the spontaneous polarization axle is along＜110〉direction orientations) or rhomboidan (wherein the spontaneous polarization axle is along＜111〉direction orientations), and shows ferroelectricity.The trend that exists is that when the difference of tolerance factor and 1.0 increased, it is higher that ferroelectricity becomes.
Table 1 shown constitute in the various mixed crystals each first and second components and the molar fraction that in various mixed crystals, realizes first and second components of morphotropy phase boundary (MPB), the tolerance factor TF of wherein said first component is greater than 1, and the tolerance factor TF of described second component is less than 1.Table 1 has also shown A-position and the beta-position ionic average ion radius in various mixed crystals, the tolerance factor TF in the various mixed crystals, by the crystallographic system of the monocrystalline of first and second each self-forming of component, A-position in monocrystalline and the tolerance factor TF of beta-position ionic ionic radius and this monocrystalline.In table 1, quadratic crystal, rhomboidal crystal and rhomboidan are represented by T, O and R respectively.
Understand that from table 1 the tolerance factor TF that the MPB of mixed crystal forms falls within 0.98 to 1.01 the scope.Owing to be confirmed as satisfying inequality (1) according to the composition of perofskite type oxide of the present invention, therefore according to the composition of perofskite type oxide of the present invention near MPB or its.
Table 1
| TF＞1 | TF＜1 | MPB | |||||||||||||
| Crystallographic system | A ionic radius | B ionic radius | TF | Mark | Crystallographic system | A ionic radius | B ionic radius | TF | Mark | A ionic radius | B ionic radius | TF | |||
| PT-PZ | PbTiO 3 | T | 1.49 | 0.61 | 1.017 | 0.48 | PbZrO 3 | R | 1.49 | 0.72 | 0.964 | 0.52 | 1.49 | 0.67 | 0.989 |
| PT-PS | PbTiO 3 | T | 1.49 | 0.61 | 1.017 | 0.45 | PbSnO 3 | R | 1.49 | 0.69 | 0.978 | 0.55 | 1.49 | 0.65 | 0.995 |
| PT-BiF | PbTiO 3 | T | 1.49 | 0.61 | 1.017 | 0.3 | BiFeO 3 | R | 1.37 | 0.55 | 1.005 | 0.7 | 1.41 | 0.57 | 1.008 |
| BT-BiNT | BT | T | 1.61 | 0.61 | 1.059 | 0.15 | (Bi，Na)TiO 3 | R | 1.38 | 0.61 | 0.978 | 0.85 | 1.41 | 0.61 | 0.990 |
| BT-BiNT | BT | T | 1.61 | 0.61 | 1.059 | 0.07 | (Bi，Na)TiO 3 | R | 1.38 | 0.61 | 0.978 | 0.93 | 1.40 | 0.61 | 0.984 |
| BT-BiNT | (Bi，K)TiO 3 | T | 1.51 | 0.61 | 1.024 | 0.2 | (Bi，Na)TiO 3 | R | 1.38 | 0.61 | 0.978 | 0.8 | 1.41 | 0.61 | 0.987 |
| KNN | KNbO 3 | O | 1.64 | 0.64 | 1.054 | 0.49 | NaNbO 3 | O | 1.39 | 0.64 | 0.967 | 0.51 | 1.51 | 0.64 | 1.010 |
For example, by at first selecting to have composition ADO
3And tolerance factor TF as first component, and has composition BEO greater than 1.0 first material
3And tolerance factor TF as second component, determines that auxiliary element C and F are so that perofskite type oxide (A, B, C) (D, E, F) O less than 1.0 second material then rightly
3Tolerance factor TF in 0.98 to 1.01 scope, can design the perofskite type oxide of satisfy condition (1) to (4) (preferably, condition (1) is to (5)).
In above-mentioned design, select the first component ADO of tolerance factor TF greater than 1.0 (that is, having high ferroelectricity)
3With the second B component EO of tolerance factor TF less than 1.0 (that is, having high ferroelectricity)
3, and definite auxiliary element C and F, so that perofskite type oxide (A, B, C) (D, E, F) O
3Composition near MPB or its.As the 3rd component CFO
3Tolerance factor TF near 1.0 o'clock (preferably in 0.98 to 1.02 scope) and the 3rd component CFO
3Ferroelectricity when reducing, can design the perofskite type oxide of satisfy condition (1) to (4) (preferably, condition (1) is to (5)).
Perofskite type oxide (A, B, C) (D, E, F) O from design according to the present invention
3Piezoelectricity (ferroelectric) performance consider, more preferably be the first component ADO
3With the second B component EO
3Ferroelectricity higher.That is, more preferably be the first component ADO
3With the second B component EO
3Tolerance factor TF separately departs from 1.0 biglyyer.
Particularly, serve as that PT (PbTiO is selected on the basis by figure with Fig. 1
3, it has the tolerance factor TF greater than 1.0) and PZ (PbZrO
3, it has the tolerance factor TF less than 1.0), for example adding then, niobium etc. can make perofskite type oxide (A, B, C) (D, E, F) O as the beta-position ion
3Tolerance factor TF reach in 0.98 to 1.01 scope.According to the figure of Fig. 1, at PbNbO
3, PT is identical with A-position ionic ionic radius among the PZ, and PbNbO
3Tolerance factor TF between PT and PZ.Therefore, by niobium being joined in the mixed crystal of PT and PZ, can make perofskite type oxide (A, B, C) (D, E, F) O
3Tolerance factor TF reach in 0.98 to 1.01 scope.In this case, the composition of perofskite type oxide becomes Pb (Ti, Zr, Nb) O
3
Consider the ionic valence state, only by PbNbO
3The crystal that forms can not have perovskite structure.In the material according to the invention design, by obtaining oxide compound ADO3, BEO in theory
3And CFO
3Tolerance factor TF separately designs total composition of perofskite type oxide, and with only by oxide compound ADO3, BEO
3And CFO
3In a kind of crystal of formation whether can to have a perovskite structure irrelevant.
Alternatively, selecting PT (PbTiO
3, it has the tolerance factor TF greater than 1.0) and PZ (PbZrO
3It has the tolerance factor TF less than 1.0) situation under, by other element such as Sn, Ta, Mo, W, Ir, Os, Pd, Pt, Re, Mn, Co, Ni, V and the Fe of various ionic radius near the ionic radius of niobium added as the beta-position ion, (preferably, condition (1) is to (5)) also can satisfy condition (1) to (4).
In addition, can also be with two or more addings among Sn, Nb, Ta, Mo, W, Ir, Os, Pd, Pt, Re, Mn, Co, Ni, V and the Fe as the beta-position ion.That is, can be expressed as such composition formula according to the composition of the above-mentioned example of perofskite type oxide of the present invention,
Pb(Ti，Zr，M)O
3， (PX)
In the formula, at mixture Pb (Ti, Zr, M) O
3In M be at least a among metallic element Sn, Nb, Ta, Mo, W, Ir, Os, Pd, Pt, Re, Mn, Co, Ni, V and the Fe.
Alternatively, can will (form (A, B, C) (D, E, F) O as A-position ionic element
3In as Elements C) join in the mixed crystal of PT and PZ, rather than add as beta-position ionic element and (forming (A, B, C) (D, E, F) O
3In as element F).In addition, alternatively, can will (form (A, B, C) (D, E, F) O as A-position ionic element
3In as Elements C) and (forming (A, B, C) (D, E, F) O as beta-position ionic element
3In as element F) all join in the mixed crystal of PT and PZ.
In addition, select BT (BaTiO by figure based on Fig. 1
3, it has the tolerance factor TF greater than 1.0) and CT (CaTiO
3, it has the tolerance factor TF less than 1.0), for example add strontium etc. then as A-position ion, also can make perofskite type oxide (A, B, C) (D, E, F) O
3Tolerance factor TF reach in 0.98 to 1.01 the scope.In this case, the composition of perofskite type oxide becomes (Ba, Ca, Sr) TiO
3
In addition, also can be with above-mentioned design A-position ion (Ba, Ca and Sr) mode be applied to the above-mentioned mixed crystal that contains as beta-position ionic Ti and Zr, and further will join and contain as beta-position ionic Ti and Zr and as the Ba of A-bit element as beta-position ionic element M, in the mixed crystal of Ca and Sr (with above-mentioned design at Pb (Ti, Zr, M) O
3In the similar mode of mode of beta-position element).In this case, the composition of perofskite type oxide can be expressed as such composition formula,
(Ba，Ca，Sr)(Ti，Zr，M)O
3， (PY)
In the formula, at mixture (Ba, Ca, Sr) (Ti, Zr, M) O
3In M be at least a among metallic element Sn, Nb, Ta, Mo, W, Ir, Os, Pd, Pt, Re, Mn, Co, Ni, V and the Fe.
In addition, select BA (BiAlO by figure based on Fig. 1
3, it has the tolerance factor TF greater than 1.0) and as the first component ADO
3And be selected from BF (BiFeO
3, it has the tolerance factor TF less than 1.0) and as the second B component EO
3, for example adding then, strontium etc. also can make perofskite type oxide (A, B, C) (D, E, F) O as the beta-position ion
3Tolerance factor TF in 0.98 to 1.01 scope.In this case, because TF (BiFeO as shown in FIG. 1
3)=0.960 and TF (BiScO
3)=0.911, so TF (BiScO
3)＜TF (BiFeO
3), and BiScO
3Do not satisfy and be not equal to (5).Yet, form by suitably regulating, can make perofskite type oxide Bi (Al, Fe, Sc) O
3Tolerance factor TF in 0.98 to 1.01 scope.(for example, (Bi (Al
0.6Fe
0.35Sc
0.05) O
3Tolerance factor TF be 0.989).Be added into conduct at perofskite type oxide Bi (Al, Fe, M) O
3In beta-position ionic element M be the ionic radius element that approaches the ionic radius of scandium (such as, Cr, Mn, Co, Ni or Ga) situation under, perofskite type oxide Bi (Al, Fe, M) O
3Also can satisfy inequality (1) to (4) (and satisfying inequality (5) in the preferred case).Therefore, the composition of this perofskite type oxide can be expressed as following composition formula,
Bi(Al，Fe，M)O
3， (PW)
In the formula, at mixture Bi (Al, Fe, M) O
3In M be at least a among metallic element Cr, Mn, Co, Ni, Ga and the Sc.
According to the present invention, obtain oxide compound (A, B, C) (D, E, F) O in theory
3, ADO
3, BEO
3And CFO
3In each tolerance factor, determine perofskite type oxide (A, B, C) (D, E, F) O then
3Composition.At this moment, even when they self do not form perovskite structure, also obtain the tolerance factor of each oxide compound in theory, then, obtain perofskite type oxide (A, B, C) (D, E, F) O when one or more oxide compounds
3Composition, with satisfy condition (1) to (4) (preferably, condition (1) is to (5)).Perofskite type oxide according to above-mentioned material principle of design design has at MPB or near the composition it, therefore shows high piezoelectricity (ferroelectric) performance.
As explanation in " summary of the invention ", the phase structure of perofskite type oxide has no particular limits.For example, perofskite type oxide can have wherein three component ADO
3, BEO
3And CFO
3The three-phase mixed-crystal structure of coexistence, perhaps three component ADO wherein
3, BEO
3And CFO
3Solid solution becomes monophasic phase structure, perhaps other structure fully.
Preferably, perofskite type oxide according to the present invention contains tolerance factor TF greater than 1.0 the first component ADO
3, tolerance factor TF is less than 1.0 the second B component EO
3And tolerance factor TF is near 1.0 the 3rd component CFO
3As previously described, at the first component ADO
3, the second B component EO
3With the 3rd component CFO
3In each component in, the molar weight of A-bit element and the molar weight of beta-position element are generally 1: 3 with respect to the ratio of the molar weight of Sauerstoffatom separately, however at the first component ADO
3, the second B component EO
3With the 3rd component CFO
3Can form separately in the scope of perovskite structure, the molar weight of A-bit element and the molar weight of beta-position element can depart from 1: 3 with respect to the ratio of the molar weight of Sauerstoffatom separately.
Further preferably, the first component ADO
3With the second B component EO
3Form respectively corresponding to the structure of the isomorphous system not, and especially preferredly be the first component ADO
3, the second B component EO
3With the 3rd component CFO
3Form respectively corresponding to the structure of the isomorphous system not.
In a preferred embodiment of perofskite type oxide, the first component ADO
3Crystallographic system be square, oblique a kind of in side, monocline, three parts and the rhombohedral system, the second B component EO
3Crystallographic system be to be different from the first component ADO
3Pros, oblique a kind of in side and the rhombohedral system, and the 3rd component CFO
3Be cube and false isometric system in a kind of.
When designing perofskite type oxide according to the present invention, can prepare the perofskite type oxide that has at MPB or near composition it and mixed-crystal structure, described mixed-crystal structure by be selected from pros, tiltedly at least two kinds of crystalline phases in side and the rhombus crystalline phase and be selected from cube and false cube crystalline phase at least a crystalline phase constitute.
In addition, when designing perofskite type oxide according to the present invention, can also prepare the perofskite type oxide that has at MPB or near the composition it, and this perofskite type oxide in high resolving power X-ray diffraction (XRD) figure, demonstrate tetragonal phase first diffraction peak, rhombus crystalline phase second diffraction peak and be different from the 3rd diffraction peak of first and second diffraction peaks.
The inventor has carried out the measurement of high resolving power XRD, and confirm to form and to form the three-phase mixed-crystal structure at MPB or near the Nb-doping PZT (Nb-PZT) it, in this three-phase mixed-crystal structure, tetragonal phase and rhombus crystalline phase and be different from this tetragonal phase and the third phase of rhombus crystalline phase coexistence (as the specific embodiment 1 with reference to Fig. 9 A is illustrated below).Nb-PZT can be expressed as composition formula Pb (Ti, Zr, M) O
3Oxide compound in a kind of, and be the perofskite type oxide that satisfies above-mentioned condition (1) to (5).On the other hand, forming in MPB or near the not doping PZT it, do not having the diffraction peak (as below comparative example 1 with reference to Fig. 9 B illustrated) of discovery corresponding to third phase.
The verified such fact of the inventor, the tolerance factor TF of the 3rd component is near 1.0, and the lattice parameter of the phase of the 3rd component that obtains from the corresponding diffraction peak of high resolving power XRD with when the 3rd component be assumed that mutually cube or during vacation cube crystalline phase desired lattice parameter conform to.Based on result's (as specific embodiment 1 and the table 2 with reference to Fig. 9 A is illustrated below) that the above-mentioned fact and EXAFS (expansion X-gamma absorption fine structure) measure, the inventor infer this third phase for cube or false cube crystalline phase.
The inventor is verified, and the perofskite type oxide according to the present invention with three-phase mixed-crystal structure is so a kind of material: it shows high piezoelectric property and can be used for effectively as in the system that utilizes the inductive phase transformation of electric field institute that is proposed at Japanese unexamined patent publication 2007-116091.
2. the characteristic of piezoelectrics
Below, explain as in the system that utilizes the phase transformation of electric field inductive that Japanese unexamined patent publication 2007-116091 is proposed.This system comprises the piezoelectrics with first ferroelectric phase, and described first ferroelectric phase is formed on the structure in first crystallographic system.When piezoelectrics apply electric field, at least a portion of first ferroelectric phase be transformed into second ferroelectric phase mutually, described second ferroelectric phase is formed on the structure in second crystallographic system that is different from first crystallographic system.
At first, the piezoelectric property of explained later piezoelectrics, for the purpose of simplifying the description, suppose that originally whole piezoelectrics all are in first ferroelectric phase, when when these piezoelectrics apply electric field, first ferroelectric phase is transformed into second ferroelectric phase, and the structure in first ferroelectric phase and structure in second ferroelectric phase are corresponding to different crystallographic systems.Fig. 2 has schematically shown the relation between (by line Y, Z and X) strength of electric field and the deflection in piezoelectrics.
In Fig. 2, E1 is the field minimum intensity of above-mentioned first ferroelectric phase when beginning phase transformation, and the strength of electric field that E2 is phase transformation when finishing basically.Described " strength of electric field when phase transformation is finished basically " also no longer produces the strength of electric field of a kind of like this level of phase transformation even be to become when being higher than this level when strength of electric field.In some cases, even be higher than E2 when strength of electric field becomes, first ferroelectric phase of a part does not undergo phase transition yet, thereby this part still is in first ferroelectric phase.
In 0 to E1 first scope, because the piezoelectric activity in first ferroelectric phase (before the phase transformation), the deflection of piezoelectrics is linear increase (shown in the line Y among Fig. 2) with the increase of strength of electric field at electric field strength E.In second scope of electric field strength E from E1 to E2, because the change of the crystalline structure relevant with phase transformation has caused the stereomutation of piezoelectrics, the deflection of piezoelectrics is with still linear increase (shown in the line Z among Fig. 2) of the increase of strength of electric field.In three scope of electric field strength E greater than E2, because the piezoelectric activity in second ferroelectric phase (after the phase transformation), the deflection of piezoelectrics is linear increase (shown in the line X among Fig. 2) with the increase of strength of electric field still.
As mentioned above, the change of the crystalline structure relevant with phase transformation has caused the stereomutation of piezoelectrics, and since piezoelectrics before phase transformation and all be in ferroelectric phase afterwards, so the piezoelectric effect of ferroelectric substance all works before phase transformation and afterwards.Therefore, can realize big distortion in second scope of 0 to E1 first scope, E1 to E2 with in according to piezoelectrics of the present invention greater than each scope in the 3rd scope of E2.
In addition, Fig. 2 has also schematically illustrated the piezoelectric property of the piezoelectrics in the conventional piezo-electric device of the disclosed first kind in JP2006-36578A, and in JP3568107 the piezoelectric property of the piezoelectrics in the conventional piezo-electric device of disclosed second class.Particularly, in first scope of strength of electric field (0≤E≤E1), the piezoelectric property of the piezoelectrics in the conventional piezo-electric device of the first kind piezoelectric property with piezoelectrics in the piezo-electric device that JP2007-116091A proposed basically is identical, and in the second and the 3rd scope of strength of electric field (E1≤E), the piezoelectric property that is different from the piezoelectrics in the piezo-electric device that proposes at JP2007-116091A, and the piezoelectric property of the piezoelectrics in the conventional piezo-electric device of the first kind (part of E1≤E) is represented by thick some dash line Y in the second and the 3rd scope of strength of electric field.In addition, in first and second scopes of strength of electric field (0≤E≤E2), the piezoelectric property of the piezoelectrics in the conventional piezo-electric device of second class piezoelectric property with piezoelectrics in the piezo-electric device that JP2007-116091A proposed basically is identical, and in the second and the 3rd scope of strength of electric field (E2≤E), the piezoelectric property that is different from the piezoelectrics in the piezo-electric device that proposes at JP2007-116091A, and (part of E2≤E) is represented by the solid line Z of 2 thick dash lines in the 3rd scope of piezoelectric property in strength of electric field of the piezoelectrics in the conventional piezo-electric device of second class.
As the front the description in " background technology ", in the conventional piezo-electric device of the above-mentioned first kind, usually by electric field is imposed on ferroelectrics along the spontaneous polarization direction, in order to the expansible piezoelectric activity that is used on the spontaneous polarization direction.That is, in the conventional piezo-electric device of the first kind, before strength of electric field reached predeterminated level, the deflection of piezoelectrics is linear increase (as shown in the line Y of Fig. 2) with the increase of strength of electric field.Yet when strength of electric field surpassed predeterminated level, the increasing amount of distortion significantly reduced, and deflection is almost saturated.
In addition, the description in " background technology ", Japanese Patent 3568107 only discloses the piezoelectrics that utilize the phase transformation between ferroelectric phase and paraelectric phase basically as the front.In Japanese Patent 3568107 in the disclosed piezo-electric device, reach degree (as the electric field strength E in Fig. 2 1) that phase transformation begins before in strength of electric field, because the piezoelectric activity in first ferroelectric phase (before the phase transformation), the deflection of piezoelectrics increases (shown in the line Y among Fig. 2) with the increase of strength of electric field.Then, reach degree (as the electric field strength E among Fig. 2 2) that phase transformation finishes basically before in strength of electric field, because the change of the crystalline structure relevant with phase transformation has caused the stereomutation of piezoelectrics, so the deflection of piezoelectrics further increases (representing as the line Z among Fig. 2) with the increase of strength of electric field.Yet during degree (as the electric field strength E among Fig. 2 2) when strength of electric field surpasses phase transformation and finishes basically, piezoelectric effect is inoperative, thereby deflection no longer further increases.
On the other hand, when when piezoelectrics apply electric field, be transformed into corresponding to the piezoelectrics of second ferroelectric phase of second crystallographic system corresponding to first ferroelectric phase of first crystallographic system and can realize than the bigger deflection of piezoelectrics in the conventional piezo-electric device of the first and second above-mentioned types.Although the activation to piezoelectrics does not apply special condition, consider deflection, preferably, activate piezoelectrics, make field minimum intensity Emin and maximum field intensity Emax satisfy the condition of inequality (6) expression.
Emin＜E1＜Emax (6)
In addition, especially preferred is that the activation piezoelectrics make field minimum intensity Emin and maximum field intensity Emax satisfy the condition of inequality (7) expression.
Emin＜E1≤E2＜Emax (7)
In addition, preferably, the ferroelectric phase that undergoes phase transition is along having crystalline orientation on the direction that is different from the spontaneous polarization orientation, and more preferably is, the ferroelectric phase phase transformation after along with phase transformation after the spontaneous polarization axle be orientated on much at one the direction and have crystalline orientation.Normally, crystalline orientation equals to apply the direction of electric field.Especially preferably make the direction and the orientation of the spontaneous polarization axle after the phase transformation approximately equal that apply electric field, because in this case, the structural domain effect of design can work before the phase transformation and make phase transformation before deflection greater than by making the direction that applies electric field equate the deflection of realizing with spontaneous polarization axle orientation before the phase transformation.Following document is explained the structural domain effect of the design in monocrystalline: S.E.Park etc., " Ultrahigh strain and piezoelectric behavior inrelaxor based ferroelectric single crystals; " Journal of Applied Physics, 82 volumes, the 1804-1811 page or leaf, 1997.
And, when the direction that applies electric field is orientated near the spontaneous polarization axle after equaling phase transformation, can easily undergo phase transition.The inventor thinks, because the state that equals spontaneous polarization axle orientation in the direction that applies electric field is stable on the crystallography, thereby can easily take place to the more transformation of steady state.In some cases, even when the electric field that will be higher than electric field strength E 2 imposes on piezoelectrics, in a part of ferroelectric phase, do not undergo phase transition yet.Yet, when phase transformation can easily take place, even can reduce the ferroelectric phase part that when the electric field that will be higher than electric field strength E 2 imposes on piezoelectrics, does not also undergo phase transition.Therefore, under the situation of the direction that applies electric field, under the situation than the orientation of the spontaneous polarization axle before equaling phase transformation in the direction that applies electric field, can stably realize bigger distortion near the orientation of the spontaneous polarization axle after equaling phase transformation.
And, be orientated near equaling phase transformation spontaneous polarization axle afterwards because apply the direction of electric field, so work effectively in the ferroelectric phase of piezoelectric activity after phase transformation, thereby can stably realize big deformation.
As mentioned above, under the situation that the direction that applies electric field is orientated near the spontaneous polarization axle after equaling phase transformation, can be before phase transformation, in the process and realize big distortion afterwards.This effect is worked when the spontaneous polarization axle before the direction that applies electric field is different from phase transformation is orientated at least, and becomes more outstanding when the direction that applies electric field is orientated near the spontaneous polarization axle after the phase transformation.
In the above description, suppose that piezoelectrics have the phase structure that only contains corresponding to single first ferroelectric phase of first crystallographic system, when when these piezoelectrics apply electric field, described first ferroelectric phase is transformed into second ferroelectric phase corresponding to second crystallographic system that is different from first crystallographic system.Yet above-mentioned explanation can also be applied to have the piezoelectrics that contain corresponding to a kind of mixed-crystal structure of ferroelectric phase of crystallographic system, and when when these piezoelectrics apply electric field, described ferroelectric phase is transformed into corresponding to the another kind of ferroelectric phase of the isomorphous system not.
3. phase transformation pattern 1
The inventor finds, has by the first component ADO
3, the second B component EO
3With the 3rd component CFO
3The three-phase mixed-crystal structure that constitutes can be used for above-mentioned utilization effectively by applying the system of electric field institute inductive phase transformation according to perofskite type oxide of the present invention.Hereinafter, with reference to figure 3A, 3B and 3C, the phase transformation pattern 1 that will be in the phase transformation interpretation of scheme in the three-phase mixed-crystal structure, Fig. 3 A, 3B and 3C have illustrated the exemplary status by the three-phase mixed-crystal structure that constitutes corresponding to the structural domain of three kinds of crystallographic systems in the phase transformation pattern 1.In phase transformation pattern 1, first component forms quadratic crystal (T), and second component forms rhomboidan (R), and the 3rd component forms false cubic system (PC).
Although a kind of in first and second components or the ferroelectric phase of each can be transformed into corresponding to the different ferroelectric phases of the isomorphous system not, second component changed into the situation of tetragonal phase (T) as an example following explanation from rhombus crystalline phase (R).In addition, in following example, the ferroelectric phase of first component has along the crystalline orientation of spontaneous polarization axle orientation (promptly, spontaneous polarization axle orientation along the ferroelectric phase of first component applies electric field), and after the phase transformation, the ferroelectric phase of second component has near the crystalline orientation (that is, applying the spontaneous polarization axle orientation of the direction of electric field near the ferroelectric phase that equals phase transformation second component afterwards) along spontaneous polarization axle orientation.In Fig. 3 A, 3B and 3C, the solid line of band arrow is represented the direction of polarization in corresponding construction territory, and the hollow arrow that has symbol " E " is represented the direction and the strength of electric field of the electric field that applies.
As shown in Figure 3A, when there not being piezoelectrics to apply electric field (promptly to perofskite type oxide with above-mentioned three-phase mixed-crystal structure, as E=0) time, the diamond structure territory D2 of the square structure territory D1 of first component and second component shows ferroelectricity, and the false cubic structure territory D3 of the 3rd component does not show ferroelectricity.
The inventor thinks, surpass above-mentioned field minimum intensity E1 (under this strength of electric field when shown in Fig. 3 B, applying not to piezoelectrics, the phase transformation of ferroelectric structural domain begins) the electric field E of low strength of electric field the time, at first, the false cubic structure territory D3 of the 3rd component is converted to the ferroelectric structural domain that has along the spontaneous polarization axle of the direction of an electric field that applies.In the example shown in Fig. 3 B, the whole false cubic structure territory D3 of the 3rd component changes square structure territory (T) into.Yet in some cases, a part of false cubic structure territory D3 may not change, thereby can remain false cubes.
The inventor thinks, is induced and promoted the variation of the square structure territory D1 of first component and the structural domain D2 of second component (abutment structure territory D3) by the caused displacement in the false cubic structure territory D3 of the 3rd component of the transformation of structural domain D3.
In the diamond structure territory D2 of second component of TF＜1.0, the beta-position ion is greater than A-position ion, thereby the beta-position ion can not easily move.On the other hand, in the square structure territory D1 of first component of TF＞1.0, the beta-position ion is less than A-position ion, thereby the beta-position ion can relatively easily move.Therefore, the inventor thinks, the transformation of square structure territory D1 that is caused first component under low strength of electric field by the caused displacement in the structural domain D3 of the 3rd component of the transformation of structural domain D3 is greater than the transformation of the diamond structure territory D2 of second component, therefore, structural domain D1 can more easily expand along spontaneous polarization axle orientation than structural domain D2.
The inventor also thinks, when strength of electric field further increases, the displacement in the false cubic structure territory D3 of the 3rd component that causes by the transformation of structural domain D3 and/or induce and promote the transformation of the diamond structure territory D2 of second component to tetragonal phase (T) because of the transformation of structural domain D1 causes displacement in the D1 of the square structure territory of first component.Fig. 3 C has shown the state of piezoelectrics that intensity E is higher than the electric field of electric field strength E 2 (under this strength of electric field, the phase transformation of ferroelectric phase is finished basically) that applies.Although in the example shown in Fig. 3 C, entire structure territory D2 has been transformed into tetragonal phase (T), and in some cases, the structural domain D2 of a part can not change, and can remain rhombus.
Fig. 4 A be schematically illustrate potential energy and in the structure cell of rhomboidan the figure of the relation the distance from the center to the beta-position element, and Fig. 4 B be schematically illustrate potential energy and cube or the structure cell of false cubic system in the figure of relation the distance from the center to the beta-position element.Shown in Fig. 4 A, in the time of on the beta-position ion is in slightly away from two positions at structure cell center, rhombus (R) crystalline potential energy minimum (that is, rhomboidan is the most stable).On the other hand, shown in Fig. 4 B, when the center of beta-position ion at structure cell, cube (C) or false cube (PC) crystalline potential energy minimum (that is, cube or false cubic system be the most stable).
In addition, Fig. 4 B shows that when the beta-position ion moved away from the center of structure cell slightly, the slope of cube (C) or false cube (PC) crystalline potential curve was mild relatively.Therefore, can think that the beta-position ion in cube (C) or false cube (PC) crystal can relatively easily move under low strength of electric field, therefore in cube (C) or false cube (PC) crystal, can more easily undergo phase transition.On the other hand, Fig. 4 A shows that when the beta-position ion moved away from the center of structure cell slightly, the slope of rhombus (R) crystalline potential curve was steeper relatively.Therefore, can think, beta-position ion ratio in rhombus (R) crystal may more be not easy to move in cube (C) or false cube (PC) crystal, and therefore ratio may more be not easy to undergo phase transition in cube (C) or false cube (PC) crystal in rhombus (R) crystal.Yet the inventor thinks that the existence of the phase that the structural domain D3 of the 3rd component promptly at first changes has promoted the phase transformation in rhombus (R) crystal.
Than the conventional equipment that does not undergo phase transition or only take place the phase transformation from the ferroelectric phase to the paraelectric phase, phase transformation according to the present invention is subjected to electric field to apply the inductive system can realize higher piezoelectric property.In addition, the inventor thinks, phase transformation among the ferroelectric structural domain D1 that the existence of the phase that the structural domain D3 of the 3rd component promptly at first changes has promoted in first component and the ferroelectric structural domain D2 of second component is even therefore hanging down under the strength of electric field, also can realize higher piezoelectric property.
Although as mentioned above, being considered to mutually of the structural domain D3 of the 3rd component at first changes, and when not when piezoelectrics apply electric field, the structural domain D3 of the 3rd component is considered to para-electric.Therefore, field minimum intensity E1 (under this strength of electric field, the phase transformation of ferroelectric phase begins) is the field minimum intensity of beginning phase transformation in any in the ferroelectric structural domain D2 of the ferroelectric structural domain D1 of first component and second component.
As illustrated based on specific embodiment 2 and comparative example 2 after a while, the inventor is verified than having at MPB or near the composition it only by the not doping PZT of the two-phase mixed-crystal structure of PT (as first component) and PZ (as second component) formation, even under low strength of electric field, have at MPB or near the composition it by PT (as first component), PZ (as second component) and PbNbO
3The Nb-doping PZT (Nb-PZT) of the three-phase mixed-crystal structure that (as the 3rd component) constitutes also can realize high piezo-electric modulus.
4. phase transformation pattern 2
Even the perofskite type oxide in the design according to the present invention has the phase structure that is different from the three-phase mixed-crystal structure, this perofskite type oxide also can be used for utilizing the system that applies the inductive phase transformation of electric field institute effectively.The inventor has prepared has Nb-doping PZT (Nb-PZT) film that is mainly formed and contain some tetragonal phases in MPB or near the composition it and phase structure by the rhombus crystalline phase, and verified this Nb-PZT film can be used for utilizing the system that applies the inductive phase transformation of electric field institute effectively, even and under low strength of electric field, also can have high piezo-electric modulus, these as specific embodiment 3 below as described in.Hereinafter, with reference to figure 5A, 5B and 5C, will in the phase transformation interpretation of scheme in the above-mentioned phase structure phase transformation pattern 2, described Fig. 5 A, 5B and 5C have illustrated the exemplary status of the mixed-crystal structure that is made of the structural domain corresponding to two kinds of crystallographic systems of phase transformation pattern 2.In phase transformation pattern 2, when not applying electric field, piezoelectrics mainly are made of rhombus crystalline phase (R), and when applying electric field, rhombus crystalline phase (R) changes tetragonal phase (T) into.In addition, in following example, ferroelectric phase (R) has the crystalline orientation (that is, the orientation of the electric field that applies is approximately equal to the orientation of the spontaneous polarization axle of phase transformation ferroelectric phase afterwards) that is orientated near the spontaneous polarization axle along tetragonal phase (T).
The inventor thinks that the phase transformation in phase transformation pattern 2 is performed as follows.
When not when the piezoelectrics of the perofskite type oxide with above-mentioned phase structure apply electric field (that is, as E=0), piezoelectrics are mainly formed by diamond structure territory (R), and because mixture (A, B, C) (D, E, F) O
3In be doped with Elements C and F, thereby shown in Fig. 5 A, in diamond structure territory (R), be formed with square nanostructure territory (T).
Above-mentioned square nanostructure territory (T) becomes the seed (starting point) of phase transformation.Promptly, when applying, the piezoelectrics to the phase structure that originally has Fig. 5 A have the field minimum of being equal to or higher than intensity E1 (under this strength of electric field, begin the phase transformation of ferroelectric structural domain (R)) the electric field of medium tenacity E the time, promptly, when E1≤E≤E2, the phase transformation in diamond structure territory (R) develops from square nanostructure territory (T), thereby shown in Fig. 5 B, forms the big square structure territory (T) of ratio nano structural domain on every side in the nanostructure territory.
Afterwards, when strength of electric field further increased, above-mentioned to the phase-change induced of bigger square structure territory (T) and promoted displacement and phase transformation in residual ferroelectric structural domain (R) part, the result produced by the big distortion of electric field institute inductive.Fig. 5 C shown when when piezoelectrics apply the electric field of the intensity that is not less than electric field strength E 2 (under this strength of electric field, the phase transformation of ferroelectric structural domain (R) is finished basically), that is, when E 〉=E2, the state of these piezoelectrics.Although whole diamond structure territory (R) has been converted to tetragonal phase (T), in some cases, a part of diamond structure territory (R) may not change, and remains rhombus.
As mentioned above, the present invention proposes a kind of novel material principle of design that preparation has the perofskite type oxide of excellent piezoelectricity (ferroelectric) performance that is used for.Therefore,, can easily design composition, so that this perofskite type oxide shows excellent piezoelectricity (ferroelectric) performance at MPB or near the perofskite type oxide it according to the present invention.
Especially, the perofskite type oxide of material according to the invention principle of design preparation is suitable for using in the utilization that is proposed as Japanese unexamined patent publication 2007-116091 applies the system of electric field institute inductive phase transformation.According to the present invention, has the perofskite type oxide that under low strength of electric field, also can easily undergo phase transition and can realize the structural domain structure of gross distortion even can provide.The feature that realizes gross distortion under low strength of electric field is preferable for saving energy.
5. ferroelectricity mixture
As previously described, ferroelectricity mixture according to the present invention is characterised in that and comprises the perofskite type oxide that it forms the design of material according to the invention principle of design.Except that perofskite type oxide according to the present invention, can further comprise component arbitrarily according to ferroelectricity mixture of the present invention, such as being different from the perofskite type oxide according to perofskite type oxide of the present invention, another kind of doping agent, agglutinant etc.
6. piezo-electric device and ink jet print head
As previously described, piezo-electric device according to the present invention is characterised in that and comprises according to piezoelectrics of the present invention and the electrode that is used for electric field is imposed on piezoelectrics.Because piezo-electric device according to the present invention has used according to perofskite type oxide of the present invention, therefore piezo-electric device according to the present invention shows high piezoelectric property.
For example, the perofskite type oxide according to the present invention that uses in the piezoelectrics of this piezo-electric device has by tolerance factor TF greater than 1.0 the first component ADO
3, tolerance factor TF is less than 1.0 the second B component EO
3And tolerance factor TF is near 1.0 the 3rd component CEO
3The three-phase mixed-crystal structure that constitutes, and a kind of in first and second components or the ferroelectric phase of each response electric field are converted under the situation of the another kind of ferroelectric phase with different crystal structure applying of piezoelectrics, even under low strength of electric field, this piezo-electric device also shows high piezoelectric property.Hereinafter, the structure of the ink jet print head (as liquid discharge device) of above-mentioned piezo-electric device and this piezo-electric device of use is explained with reference to Fig. 6, Fig. 6 has schematically shown the cross section of the necessary part of the ink jet print head that contains above-mentioned piezo-electric device, and wherein this transverse cross-section parallel is in the thickness direction of piezo-electric device.In Fig. 6, each element schematically is described, and illustrated size of component is different from the size of real system.
As shown in Figure 6, ink jet print head 3 comprises piezo-activator 2, and piezo-activator 2 is realized by using piezo-electric device 1.Piezo-electric device 1 is by form the device that lower electrode 12, piezoelectrics 13 and upper electrode 14 prepare in order in substrate 11.Piezoelectrics 13 are the polycrystal that formed by the designed perofskite type oxide of foregoing material according to the invention principle of design, but these piezoelectrics can comprise unavoidable impurities.
There is no particular limitation to be used for the material of substrate 11.For example, substrate 11 can be by preparations such as silicon, glass, stainless steel, YSZ (zirconium white that yttrium is stable), aluminum oxide, sapphire, silicon carbide.In addition, substrate 11 can realize that such as SOI (silicon-on-insulator) substrate described SOI (silicon-on-insulator) substrate is by forming SiO in order on the surface of silicon base by stacked substrate
2Oxide film and Si active layer and preparing.
In addition, the main ingredient of lower electrode 12 has no particular limits, and for example can be metal such as Au, Pt and Ir and metal oxide be such as IrO
2, RuO
2, LaNiO
3And SrRuO
3In a kind of or the combination.In addition, the main ingredient of upper electrode 14 has no particular limits, and for example can be and the example identical materials of lower electrode 12 main ingredients and a kind of or combination in common other material (such as Al, Ta, Cr or Cu) that uses in the electrode of semiconductor technology.And the thickness of bottom and upper electrode 12 and 14 has no particular limits, and is preferably 50 to 500nm.
Piezo-activator 2 comprises barrier film 16 and controller 15 and piezo-electric device 1.Barrier film 16 is attached to the back of the body surface of substrate 11, so that barrier film 16 vibrates according to the expansion and the contraction of piezoelectrics 13.Controller 15 comprises and is used to driving circuit that drives piezo-electric device 1 etc.
Ink jet print head 3 prepares by the back of the body surface that injection nozzle 20 is attached to piezo-activator 2.Injection nozzle 20 is the parts that are used to lay in and discharge China ink, and comprises black chamber 21 (as the liquid storage chamber) and China ink outlet 22 (as the liquid discharge outlet).China ink chamber 21 deposit China inks, and the China ink that will remain in the black chamber 21 gives off black chamber 21 by the China ink outlet 22 that is connected with black chamber 21.
In above-mentioned ink jet print head 3, the strength of electric field that imposes on piezo-electric device 1 increases or reduces, so that piezoelectric element expands or the discharging and the quantity discharged of contraction and control China ink.
Alternatively, the some parts of substrate 11 can be worked into the inside of barrier film 16 and injection nozzle 20, rather than barrier film 16 and injection nozzle 20 are attached to piezo-electric device 1.For example, under the situation that substrate 11 is realized such as the SOI substrate by stacked substrate, China ink chamber 21 can form by the corresponding section etching with the lower surface of substrate 11, and other structure of barrier film 16 and injection nozzle 20 can itself form by processing substrate 11.
Can suitably set the form of piezoelectrics 13.For example, piezoelectrics 13 can have the form of film or sintered ceramic body.In the first-class field of ink-vapor recording, in order to improve picture quality, current technology of just settling piezoelectric element (device) on research intensive ground.The density increase of settling with piezoelectric element interrelates, and the technology that is used to reduce the thickness of piezo-electric device is also studied.In order to reduce the thickness of piezo-electric device, piezoelectrics 13 are preferably piezoelectric film, and more preferably thickness is 20nm or littler thin piezoelectric film.Because thin piezoelectric film need have high piezo-electric modulus, and perofskite type oxide according to the present invention has high piezo-electric modulus, therefore can be effectively with the material that acts on thin piezoelectric film according to perofskite type oxide of the present invention.
According to embodiment of the present invention, piezoelectrics 13 can have by tolerance factor TF greater than 1.0 the first component ADO
3, tolerance factor TF is less than 1.0 the second B component EO
3With tolerance factor TF near 1.0 the 3rd component CFO
3The three-phase mixed-crystal structure that constitutes, and a kind of in first and second components or the ferroelectric phase response electric field of each are converted to the another kind of ferroelectric phase with different crystal structure to the applying of piezoelectrics.
For example, piezoelectrics 13 have by composition formula (PX) or (PY) expression form.
Pb(Ti，Zr，M)O
3， (PX)
(Ba，Ca，Sr)(Ti，Zr，M)O
3， (PY)
At composition formula (PX) or (PY), M is at least a among metallic element Sn, Nb, Ta, Mo, W, Ir, Os, Pd, Pt, Re, Mn, Co, Ni, V and the Fe.
According to the present embodiment, preferably, ferroelectric phase or response electric field apply and change have crystalline orientation mutually.More preferably, the crystalline orientation of each ferroelectric phase of transformation is all along the direction that is different from the spontaneous polarization axle orientation in the ferroelectric phase, and especially preferably, crystalline orientation is approximate identical with the orientation of phase transformation spontaneous polarization axle afterwards.According to the present embodiment, crystalline orientation is identical with the direction of the electric field that imposes on these piezoelectrics.
The spontaneous polarization axle of ferroelectric substance in tetragonal spheroidal＜001, in rhombic system＜110 and in rhombohedral system＜111.When a kind of in first and second components or the ferroelectric phase of each be approximate tetragonal phase, the crystalline orientation of approximate tetragonal phase, the crystalline orientation of approximate rhombus crystalline phase, the crystalline orientation of approximate rhombus crystalline phase, the crystalline orientation of crystalline orientation along＜111〉direction along＜110〉direction along＜110〉direction along＜100〉direction approximate along＜100〉direction iris mutually and crystalline orientation approximate during along a kind of in mutually of＜111〉direction iris, the direction of an electric field that imposes on piezoelectrics is equated with phase transformation spontaneous polarization axle afterwards.
For example, the piezoelectrics 13 with crystalline orientation can be alignment films (having uniaxial orientation), oriented growth grow nonparasitically upon another plant film (having three orientations) or grain-oriented sintered ceramic body.Can prepare under the uniaxial orientation crystalline condition, by using a kind of known film formation technology can form alignment films, described known film formation technology comprises gaseous techniques and liquid technology, wherein gaseous techniques comprises sputter, MOCVD (Metalorganic chemical vapor deposition), pulsed laser deposition etc., and liquid technology comprises sol-gel technique, MOD (organo-metallic decomposition) etc.For example, the platinum by using (100)-orientation etc. can be realized (100) orientation as lower electrode.By in substrate and lower electrode, using and the good material of piezoelectric film lattice match, can form the oriented growth film of growing nonparasitically upon another plant.For example, the preferred combination that is used for the material of substrate and lower electrode is SrTiO
3/ SrRuO
3, MgO/Pt etc.By hot-pressing technique, thin plate technology (sheet technique), lamination etc., can form grain-oriented sintered ceramic body.
The condition that controller 15 drives piezoelectrics 13 has no particular limits.Yet, illustrated as the front with reference to Fig. 2, consider deflection, piezoelectrics 13 are preferred by controller 15 drivings, so that field minimum intensity Emin and maximum field intensity Emax satisfy the condition of inequality (6) expression.
Emin＜E1＜Emax (6)
In addition, especially preferred is that field minimum intensity Emin and maximum field intensity Emax satisfy the condition of inequality (7) expression.
Emin＜E1≤E2＜Emax (7)
In above-mentioned inequality (6) and (7), E1 is the field minimum intensity of the phase transformation of a kind of in first and second components or the ferroelectric phase of each when beginning, and the strength of electric field that E2 is this phase transformation when finishing basically.
In addition, preferably design piezo-electric device 1 according to an embodiment of the present invention, so that, can realize phase transformation basically only by changing strength of electric field.Particularly, preferably determine the composition and the crystallographic system of piezoelectrics 13, the phase transformation between described crystallographic system is used in the piezoelectrics 13, so that phase transformation can take place under the envrionment temperature of piezoelectrics 13.Yet, in case of necessity, can regulate the working temperature of piezo-electric device 1, so that phase transformation can take place.In any case,, preferably near transformation temperature or this temperature, drive piezo-electric device 1 in order to effectively utilize this phase transformation.
Because piezo-electric device 1 according to the present invention has used the formed piezoelectrics 13 of perofskite type oxide by the design of material according to the invention principle of design, even therefore hanging down under the strength of electric field, piezo-electric device 1 also can show high piezoelectric property.
7. ink-jet recording device
Hereinafter, with reference to Fig. 7 and 8, the example of the ink-jet recording device with ink jet print head 3 is described.Fig. 7 is the synoptic diagram of ink-jet recording device example sketch map that explanation has the ink jet print head 3 of Fig. 6, and Fig. 8 is the top view of a part of the ink-jet recording device of Fig. 7.
As schematically illustrating in Fig. 7, ink-jet recording device 100 comprises print unit 102, China ink deposit and loading location 114, paper supply unit 118, decurl unit 120, assimilating type rotary conveyor 122, prints detecting unit 124 and paper output unit 126.Print unit 102 comprises a plurality of ink jet print head 3K, 3C, 3M and 3Y corresponding to different colours (black (K), cyan (C), pinkish red (M) and yellow (Y) particularly) China ink.Hereinafter, ink jet print head can be known as record-header.China ink deposit and loading location 114 deposits are supplied with the China ink of record- header 3K, 3C, 3M and 3Y.Paper supply unit 118 supply recording papers 116.Curling of recording paper 116 eliminated in decurl unit 120.Assimilating type rotary conveyor 122 is settled in the face of the nozzle face (black discharging face) of print unit 102, and feeding recordable paper 116, the planarization of the paper 116 of holding the record simultaneously.Printing detecting unit 124 reads by print unit 102 and is printed on image on the recording paper 116.Recording paper 116 after paper output unit 126 will be printed is outwards exported.
Constitute among record- header 3K, 3C, 3M and the 3Y of print unit 102 each all corresponding to ink jet print head according to embodiments of the present invention as previously described, but, in order to realize linear recording head (explained later), each ink jet print head that is used for ink-jet recording device 100 all is included in a plurality of piezo-electric devices on the lower electrode 12, and a plurality of black chamber and a plurality of China ink outlet settled according to the arrangement of a plurality of piezo-electric devices on lower electrode 12.
Use under the situation of coil paper at ink-jet recording device 100, in the stage after decurl unit 120, settle the cutting unit 128 that is used for coil paper is cut into desired size.Cutting unit 128 is made of the counteredge 128A and the blade 128B that detours.Counteredge 128A has the length of the width of the transmission route that is equal to or greater than recording paper 116, and is arranged on the side opposite with the print side of recording paper 116.With blade 128B settle relative on the print side of recording paper 116 of detouring, and move along counteredge 128A with counteredge 128A.In the ink-jet recording device that uses cutting paper, cutting unit 128 is unnecessary.
With after the coil paper decurl and cutting into recording paper 116, recording paper 116 is sent to assimilating type rotary conveyor 122.Assimilating type rotary conveyor 122 by roller 131 and 132 and endless belt 133 constitute.Roller 131 and 132 is separated to place, and endless belt 133 is by this way around roller 131 and 132 one-tenths rings: facing endless belt 133 parts of nozzle face of print unit 102 and the sensor cover of printing detecting unit 124 at least is smooth and level.
The width of endless belt 133 is greater than the width of recording paper 116, and passes endless belt 133 and form a large amount of suction orifice (not shown)s.Suction chamber 134 is arranged at the ring inside of the locational endless belt 133 relative with the sensor cover of printing detecting unit 124 with the nozzle face of print unit 102, and by blower fan 135 suctions, so that produce negative pressure in suction chamber 134, and the recording paper on endless belt 133 116 keeps by suction.
The power of electric motor (not shown) is passed in roller 131 and 132 at least one so that endless belt 133 clockwise direction in Fig. 7 drives, and will remain on recording paper 116 on the endless belt 133 in Fig. 7 from moving left the right side.
Under the situation of borderless print, China ink may be deposited on the endless belt 133.Therefore, in order to clean endless belt 133, on predetermined (suitable) position of the ring outside of endless belt 133 and print zone, arrange belt cleaning unit 136.
Among record- header 3K, 3C, 3M and the 3Y in print unit 102 each all is so-called solid line formula record-header (full-line type head), this is a kind of record-header that has corresponding to the length of the maximum width of recording paper 116, and as shown in Figure 8, this record-header is settled (that is, in the main scanning direction perpendicular to the direction of the supply of recording paper 116) across the width of recording paper 116.Particularly, among record- header 3K, 3C, 3M and the 3Y each all is so a kind of linear recording head, wherein arranges above-mentioned a plurality of black exhaust outlets (nozzle) above the length of the maximum length of dominant record paper 116 1 sides of print image in the above surpassing ink-jet recording device 100.As shown in Figure 8, corresponding to record- header 3K, 3C, 3M and the 3Y of the China ink of different colours along the direction of the supply by this series arrangement in the upstream.Therefore, in transmission log paper 116, by the China ink of discharging different colours, can be on this recording paper 116 the printing color image.
In stage after printing detecting unit 124, settle the rear portion drying unit 142 of the print surface that is used for dry recording paper 116.For example, rear portion drying unit 142 is by realizations such as heating blowers.Because before the black complete drying on the print surface, preferably avoid contact with this print surface, it is therefore preferable that rear portion drying unit 142 adds warm air and makes China ink drying on print surface by being blown into.
In order to control the glossiness that is printed on the image on the recording paper 116, the stage after rear portion drying unit 142 settle heating-and-presser unit 144.Heating-and-presser unit 144 comprises that the surface has the pressure roll 145 of predetermined projection and depression, and, pass to the print surface of recording paper 116 with projection and the depression that will be scheduled to by in the heating print surface, using this pressure roll 145 to push print surface.
At last, the print record paper 116 that produces is as mentioned above exported from paper output unit 126.Preferably with test printing product and the separately output of the actual printed product that uses.Therefore, paper output unit 126 comprises first output unit 126A of the printed product that is used for actual use and the second output unit 126B that is used for the test printing product.Although do not show, but ink-jet recording device 100 further comprises separation unit, this separation unit is the recording paper of printing hanked in 116 minutes test printing product and the actual printed product that uses, and the test printing product are sent to the second output unit 126B and the printed product of reality use is sent to the first output unit 126A.
In addition, the two is printed under the situation on the recording paper 116 simultaneously with test pattern and the actual image that uses, can settle cutting unit 148, and the second section of the first part of printing test record images paper 116 on it and the record images paper 116 that printing reality is used on it is separated.
8. specific embodiments of the invention
As described below, the inventor has prepared according to the specific embodiment 1 to 4 of piezo-electric device of the present invention and the comparative example 1 to 3 of conventional piezo-electric device.
8.1 specific embodiment 1
According to the specific embodiment 1 of piezo-electric device of the present invention by being prepared as follows.
At first, prepare wherein SiO
2Layer has the SiO of 0.1 micron thickness
2/ Si substrate.Then, at SiO
2Forming thickness in the/Si substrate is the contact layer of the titanium of 20nm, and to form thickness by sputter be the lower electrode of 0.2 micron platinum.Afterwards, 525 ℃ base reservoir temperature, forming thickness by sputter is 5.0 microns Nb-doped P ZT, Pb (Ti, Zr, Nb) O
3(PbZr particularly,
0.44Ti
0.44Nb
0.12O
3) piezoelectric film.In addition, formation thickness is the upper electrode of 0.2 micron platinum on this piezoelectric film by sputtering at.Thus, obtain according to piezo-electric device of the present invention.
8.2 comparative example 1
The comparative example 1 of piezo-electric device is by being prepared as follows.
The difference of the piezo-electric device of comparative example 1 and specific embodiment 1 is that this piezoelectric film is by unadulterated PZT (PbZr particularly,
0.52Ti
0.48O
3) make.
8.3 the comparison of specific embodiment 1 and comparative example 1
The inventor measures having carried out high resolving power X-ray diffraction (high resolving power XRD) at specific embodiment 1 and comparative example 1 piezoelectric film in separately, and the peak in the gained XRD figure is separated.Fig. 9 A and 9B have shown the high resolving power XRD figure of the piezoelectric film in specific embodiment 1 and comparative example 1 respectively.
Shown in Fig. 9 B, in the high resolving power XRD figure of the piezoelectric film of comparative example 1 (use do not mix PZT), only detect strong (200) diffraction peak of rhombus crystalline phase (R) and weak (200) diffraction peak and weak (002) diffraction peak of tetragonal phase (T).That is, confirm that the piezoelectric film in comparative example 1 has the two-phase mixed-crystal structure that is made of rhombus crystalline phase and tetragonal phase.
On the contrary, shown in Fig. 9 A, the diffraction peak that in the high resolving power XRD figure of the piezoelectric film of specific embodiment 1 (use Nb-doped P ZT), detects (200) diffraction peak of (200) diffraction peak, tetragonal phase (T) of rhombus crystalline phase (R) and (002) diffraction peak and be different from the third phase of this rhombus and tetragonal phase.
The inventor thinks that the diffraction peak of third phase is corresponding to the PbNbO that is produced by doping Nb
3Structural domain, and the inventor has been 4.08 dusts based on the lattice parameter that the diffraction peak of third phase has obtained this structural domain.This lattice parameter that is obtained is worth 4.08 dusts and works as supposition PbNbO
3Form cube or desired lattice parameter value is approximate during false cube of crystalline phase conforms to.
Then, the inventor measures by EXAFS (expansion X-gamma absorption fine structure), and separately piezoelectric film in specific embodiment 1 and the comparative example 1 has been carried out structural analysis.Figure 10 A has shown the Pb L3-border EXAFS spectrum of the piezoelectric film of the PZT that do not mix in comparative example 1, Figure 10 B is presented at the Ti K-border EXAFS spectrum of the piezoelectric film of the PZT that do not mix in the comparative example 1, Figure 10 C is presented at the Zr K-border EXAFS spectrum of the piezoelectric film of the PZT that do not mix in the comparative example 1, and Figure 10 D is presented at the Nb K-border EXAFS spectrum of the piezoelectric film of the Nb-doping PZT in the specific embodiment 1.Then, obtain the bond distance in key Ti-O, Zr-O and Nb-O, be illustrated in the table 2.
As shown in the table 2,, detect near first bond distance of 1.8 dusts with near second bond distance of 2.0 dusts for the key Ti-O in comparative example 1 and specific embodiment 1 piezoelectricity (PZT does not mix) film in separately.This means that there be (shown in Fig. 4 A) in the Ti ion with two kinds of different distance leaving the structure cell center, and PT (PbTiO
3) crystallographic system be rhombus or tetragonal spheroidal.
On the other hand, the key Nb-O in piezoelectricity (the Nb-doping PZT) film of specific embodiment 1 detects and has only a kind of bond distance.This means that the Nb ion is present in the structure cell center.Although when normally having the lattice deformability when rhombus or quadratic crystal, the Nb ion is present in the possibility at the structure cell center of rhombus or quadratic crystal, the inventor considers following practical work and infers PbNbO
3Crystallographic system be cube or false isometric system: PbNbO
3Tolerance factor (TF) near 1.0 and the lattice parameter of the third phase that obtains from the high resolving power XRD figure with work as PbNbO
3Be assumed that cube or during false cube of crystalline phase desired lattice parameter value approximate identical.
Based on the measuring result of high resolving power XRD and EXAFS, can think, the piezoelectric film that in specific embodiment 1, forms have by tetragonal phase, rhombus crystalline phase and cube or the three-phase mixed-crystal structure that constitutes of false cube crystalline phase.
Table 2
| Bond distance (_) | |||||
| Ti-O | Ti-O | Zr-O | Nb-O | ||
| |
Nb-PZT | 1.82 | 1.99 | 2.03 | 1.96 |
| Compare 1 | PZT | 1.83 | 2.01 | 2.04 | - |
8.4 specific embodiment 2
According to the specific embodiment 2 of piezo-electric device of the present invention by being prepared as follows,
At first, prepare wherein SiO
2Layer has the SiO of 0.1 micron thickness
2/ Si substrate.Then, at this SiO
2Forming thickness in the/Si substrate is the contact layer of the titanium of 20nm, and to form thickness by sputter be the lower electrode of 0.2 micron platinum.Afterwards, 525 ℃ base reservoir temperature, forming thickness by sputter is 5.0 microns Nb-doping PZT, Pb (Ti, Zr, Nb) O
3(PbZr particularly,
0.44Ti
0.44Nb
0.12O
3) piezoelectric film, then in oxygen atmosphere, in 650 ℃ of annealing.In addition, by sputter, forming thickness on this piezoelectric film is the upper electrode of 0.2 micron platinum.Thus, obtain according to piezo-electric device of the present invention.
The inventor has carried out high resolving power X-ray diffraction (high resolving power XRD) to above-mentioned piezoelectric film in specific embodiment 2 and has measured, and confirms that this piezoelectric film has the three-phase mixed-crystal structure that is similar to specific embodiment 1.In addition, the inventor carries out XRD and measures when applying electric field, and confirms when edge＜001〉part of rhombus crystalline phase (R) was transformed into tetragonal phase when direction applied electric field.Figure 11 has shown the high resolving power XRD figure of the piezoelectrics in specific embodiment 2, obtains under strength of electric field in various degree during these figure.Figure 11 explanation, when strength of electric field increases, the diffraction peak displacement of rhombus crystalline phase (R).This is because when strength of electric field increases, and the lattice of rhombus crystalline phase expands applying on the direction of electric field, thereby the lattice parameter increase.This is the piezoelectric deforming that is caused by the structural domain effect that designs.Figure 11 illustrates also that when strength of electric field increases the peak intensity of (200) of tetragonal phase (T) and (002) diffraction peak increases.This is that the part of rhombus crystalline phase (R) changes tetragonal phase into because when strength of electric field increases.
In addition, in the scope of strength of electric field between field minimum intensity Emin (=0kV/cm (＜E1)) and maximum field intensity Emax (=100kV/cm (＞E2)), the inventor utilizes cantilever to measure piezoelectric coefficient d
31, and obtained the value of 250pm/V.This piezoelectric coefficient d
31Value be the highest in the world present value known to the inventor.
8.5 comparative example 2
The comparative example 2 of piezo-electric device is by being prepared as follows.
At first, by sputter, forming thickness in (100) MgO substrate is the lower electrode of 0.2 micron platinum.Then, 525 ℃ base reservoir temperature, forming thickness by pulsed laser deposition is 5 microns not doping PZT, Pb (Ti, Zr) O
3(PbZr particularly,
0.55Ti
0.45O
3) piezoelectric film.In addition, by sputter, forming thickness on this piezoelectric film is the upper electrode of 0.2 micron platinum.Thus, obtain 2 piezoelectric film as a comparative example.
The inventor has carried out high resolving power X-ray diffraction (high resolving power XRD) to the above-mentioned piezoelectric film in comparative example 2 and has measured, and confirmed when not applying electric field, piezoelectric film is formed by the rhombus crystalline phase (R) of the crystalline orientation (the crystalline orientation degree is 95%) with edge＜001〉direction, and when＜001〉when direction applied electric field, rhombus crystalline phase (R) changed tetragonal phase (T) into.In this example, the orientation of the spontaneous polarization axle after the direction that applies electric field and the phase transformation is identical.Field minimum intensity E1 when phase transformation begins and be respectively 110kV/cm and 160kV/cm from the electric field strength E 2 of rhombus crystalline phase (R) when the phase transformation of tetragonal phase (T) is finished basically.
In addition, in the scope of field minimum intensity Emin (=50kV/cm (＜E1)) and maximum field intensity Emax (=200kV/cm (＞E2)), the inventor uses cantilever to measure the piezoelectric coefficient d of this piezoelectric film in strength of electric field
31, and the value of acquisition 190pm/V.
8.6 the comparison of specific embodiment 2 and comparative example 2
In each of specific embodiment 2 and comparative example 2, the phase transformation of ferroelectric phase has all taken place in the piezoelectric film film, and under the condition of Emin＜E1≤E2＜Emax, electric field imposes on piezoelectric film on the direction identical with the spontaneous polarization axle orientation of ferroelectric phase after the phase transformation.Although specific embodiment 2 and comparative example 2 are similarly aspect above-mentioned, to compare with the piezoelectric film that in comparative example 2, forms by the PZT that do not mix, the piezoelectric film that is formed by Nb-doping PZT in specific embodiment 2 shows bigger distortion under low electric field.That is, confirmed the effectiveness of material according to the invention principle of design.The inventor thinks that owing to use phase transformation pattern 1 to explain with reference to Fig. 3 A, 3B and 3C in front, the piezoelectric film in specific embodiment 2 shows big distortion in low strength of electric field.
8.7 specific embodiment 3
According to the specific embodiment 3 of piezo-electric device of the present invention by being prepared as follows.
At first, prepare wherein SiO
2Layer has the SiO of 0.1 micron thickness
2/ Si substrate.Then, at this SiO
2Forming thickness in the/Si substrate is the contact layer of the titanium of 20nm, and to form thickness by sputter be the lower electrode of 0.13 micron platinum.Afterwards, 525 ℃ base reservoir temperature, forming thickness by sputter is 2.4 microns Nb-doping PZT, Pb (Ti, Zr, Nb) O
3Piezoelectric film.In addition, by sputter, forming thickness on this piezoelectric film is the upper electrode of 0.2 micron platinum.Thus, obtain according to piezo-electric device of the present invention.
Piezoelectric film as specific embodiment 3 has been carried out thickness measurement to the inventor and x-ray fluorescence (XRF) is measured.Table 3 has shown the observed value of thickness and composition (molar ratio of the molar fraction of various formation elements and Zr/ (Zr+Ti)).
Table 3
| Film thickness (μ m) | Pb | Zr | Ti | Nb | Zr/(Zr+Ti) | ε | Pr (μC/cm 2) | Ec (kV/cm) | d 31 | |
| Zr+Ti+Nb＝1 | ||||||||||
| |
2.4 | 1.05 | 0.47 | 0.44 | 0.09 | 0.52 | 610 | 24.6 | 69.1 | 250 |
8.8 the evaluation of specific embodiment 3
The inventor has carried out high resolving power X-ray diffraction (high resolving power XRD) to the piezoelectric film in specific embodiment 3 and has measured, and the peak in the acquisition XRD figure is separated.Figure 12 has shown the high resolving power XRD figure and the isolating diffraction peak of the piezoelectric film in specific embodiment 3.In Figure 12, the diffraction angle of each diffraction peak (is unit with the degree), the lattice parameter that obtains based on diffraction angle and illustrate by the integrated intensity Int (%) of normalized each diffraction peak of integrated intensity at maximum diffraction peak with all being relative to each other.
As shown in figure 12, in the high resolving power XRD figure of the piezoelectric film of specific embodiment 3, detect strong (200) diffraction peak and the weak diffraction peak (it appears at the left side of strong (200) diffraction peak of rhombus crystalline phase (R)) of having only rhombus crystalline phase (R).Normally, the XRD figure with (002) diffraction peak of (200) diffraction peak of rhombus crystalline phase (R) and tetragonal phase (T) also has (200) diffraction peak of the tetragonal phase (T) on (200) diffraction peak right side of rhombus crystalline phase (R).Therefore, the XRD figure of Figure 12 is different from aforesaid common XRD figure.Therefore, the inventor thinks that this weak diffraction peak is tetragonal phase (T) (a 002) diffraction peak, and this tetragonal phase is corresponding to using phase transformation pattern 2 in front with reference to Fig. 5 A, 5B and the illustrated square structure territory that plays the effect of phase transformation seed of 5C.
The inventor has carried out the XRD measurement to the piezoelectric film in specific embodiment 3, simultaneously＜001〉piezoelectric film is applied electric field on the direction, and confirmed that rhombus crystalline phase (R) changes tetragonal phase (T) into.
And, the inventor has prepared the diaphragm type piezo-electric device as specific embodiment 3, measure relation and the relation between strength of electric field and the dielectric polarization in piezo-electric device between strength of electric field and the displacement in this piezo-electric device, and obtained to represent the curve of these relations.In the curve (electric field-displacement curve) of the relation between the displacement in expression strength of electric field and this piezo-electric device, at field minimum intensity E1 (at this, phase transformation begins) and electric field strength E 2 (at this, phase transformation finish) everywhere all have flex point (at this, the slope of electric field-displacement curve changes).Field minimum intensity E1 when the phase transformation from rhombus crystalline phase (R) to tetragonal phase (T) begins is detected as 45kV/cm, and is being detected as 67kV/cm from the electric field strength E 2 of rhombus crystalline phase (R) when the phase transformation of tetragonal phase (T) is finished basically.These all conform to the XRD measuring result of piezoelectric film when applying electric field on it based on the measuring result of electric field-displacement curve.Therefore, above-mentioned result and the XRD measurement that obtains from electric field-displacement curve confirmed the phase transformation generation.
In addition, in the scope of strength of electric field between field minimum intensity Emin (=0kV/cm (＜E1)) and maximum field intensity Emax (=100kV/cm (＞E2)), the inventor has measured the piezoelectric coefficient d of this piezoelectric film
31, and obtained the value of 250pm/V.Table 3 has also shown piezoelectric coefficient d
31Value (obtaining) by the piezo-electric device that in the scope of 0 to 100kV/cm strength of electric field, drives as specific embodiment 3 and the DIELECTRIC CONSTANT of measuring during for 100kHz in frequency.
And, by in the scope of-200 to 200kV/cm strength of electric field, driving this piezo-electric device, the inventor has obtained to be illustrated in the curve as strength of electric field in the piezo-electric device of specific embodiment 3 and the relation between the dielectric polarization, and measured the value of residual dielectric polarization Pr (measuring when strength of electric field equals zero) and coercivity electric field ec, these also all are illustrated in the table 3.
8.9 specific embodiment 4
4 by being prepared as follows according to a particular embodiment of the invention.
The inventor has designed and has been used for perofskite type oxide Bi (A1, Fe, Sc) O
3The material of film, it is by selecting BiAlO
3(tolerance factor TF is 1.012) is as first component (tolerance factor is greater than 1.0), BiScO
3(tolerance factor TF is 0.911) is as second component (tolerance factor TF is less than 1.0) and BiFeO
3(tolerance factor TF is 0.960) designed as the 3rd component, and based on Bi Al
0.6Fe
0.35Sc
0.05O
3Tolerance factor be that 0.989 understanding has been determined composition BiAl
0.6Fe
0.35Sc
0.05O
3(it is near MPB or its).
Then, by the film that is prepared as follows perofskite type oxide with above-mentioned composition.
At first, prepare wherein SiO
2The thickness of layer is 0.1 micron SiO
2/ Si substrate.Then, at SiO
2Forming thickness in the/Si substrate is the contact layer of the titanium of 20nm, and to form thickness by sputter be the lower electrode of 0.2 micron platinum.Afterwards, 670 ℃ base reservoir temperature, forming thickness by PLD (pulse-laser deposition) is 0.6 micron Bi (Al, Fe, Sc) O
3(BiA1 particularly,
0.6Fe
0.35Sc
0.05O
3) piezoelectric film.
The inventor carries out X-ray diffraction (XRD) to the piezoelectric film that as above forms and measures, and will be presented among Figure 13 A as the XRD figure of the piezoelectrics of specific embodiment 4.As shown in FIG. 13A, above-mentioned film is formed mutually by single uhligite, and preferred (100)/(001) orientation.What Figure 13 B showed is near the amplification of a part of XRD figure of Figure 13 A diffraction angle (2 θ) is 46 degree.Figure 13 B shows that (200) diffraction peak of above-mentioned film has left acromion, and is asymmetric.Shown in Figure 13 B, verified tetragonal phase (T) and the rhombus crystalline phase (R) of in above-mentioned film, being mixed with of the inventor.
8.10 comparative example 3
Except by tolerance factor TF being 0.973 BiAl
0.3Fe
0.65Sc
0.05O
3Preparation is as a comparative example outside 3 the piezoelectric film, with the similar fashion preparation of specific embodiment 43 Bi (Al, Fe, Sc) O as a comparative example
3Film.The inventor has carried out X-ray diffraction (XRD) measurement to the piezoelectric film of comparative example 3, and confirms that the piezoelectric film of comparative example 3 is formed mutually by single uhligite, and only observes rhombus phase (R).
9. other content
Can be preferably used in piezo-activator, the ferroelectric memory (FRAM) etc. according to piezo-electric device of the present invention, wherein said piezo-activator can be installed in ink jet print head, magnetic recording and replicating head, MEMS (MEMS (micro electro mechanical system)) device, micropump, the ultrasound probe etc.
Claims (59)
1. one kind is used to prepare the method with piezoelectric oxide of forming of being represented by following composition formula,
(A，B，C)(D，E，F)O
3，
In the formula, each among A, B, C, D, E and the F is all represented one or more metallic elements, and A, B and C represent A-bit element, D, E and F represent the beta-position element, and O represents oxygen element, when two kinds among A-bit plain A, B and the C or when identical all, beta-position element D, E are different with F, when two kinds among beta-position element D, E and the F or when identical all, plain A, B are different with C for the A-bit, and by composition formula (A, B, C) (D, E, F) O
3The composition of expression can form in the scope of perovskite structure, and the integral molar quantity of A-bit element and the integral molar quantity of beta-position element can depart from 1: 3 with respect to the ratio of the molar weight of Sauerstoffatom separately; Wherein
The composition of described perofskite type oxide satisfy condition (1), (2), (3) and (4),
0.98≤TF(P)≤1.01， (1)
TF(ADO
3)＞1.0， (2)
TF (BEO
3)＜1.0, and (3)
TF(BEO
3)＜TF(CFO
3)＜TF(ADO
3)， (4)
Wherein, TF (P) is by composition formula (A, B, C) (D, E, F) O
3The tolerance factor of the piezoelectric oxide of expression, TF (ADO
3) be by composition formula ADO
3The tolerance factor of the mixture of expression, TF (BEO
3) be by composition formula BEO
3The tolerance factor of the mixture of expression, and TF (CFO
3) be by composition formula CFO
3The tolerance factor of the mixture of expression.
2. method according to claim 1 is wherein determined the described composition of described perofskite type oxide, with further satisfy condition (5),
0.98≤TF(CFO
3)≤1.02 (5)。
3. piezoelectric oxide, it had by forming that following composition formula is represented,
(A，B，C)(D，E，F)O
3，
In the formula, each among A, B, C, D, E and the F is all represented one or more metallic elements, and A, B and C represent A-bit element, D, E and F represent the beta-position element, and O represents oxygen element, when two kinds among A-bit plain A, B and the C or when identical all, beta-position element D, E are different with F, when two kinds among beta-position element D, E and the F or when identical all, plain A, B are different with C for the A-bit, and by composition formula (A, B, C) (D, E, F) O
3The composition of expression can form in the scope of perovskite structure, and the integral molar quantity of A-bit element and the integral molar quantity of beta-position element can depart from 1: 3 with respect to the ratio of the molar weight of Sauerstoffatom separately; Wherein
The composition of described perofskite type oxide satisfy condition (1), (2), (3) and (4),
0.98≤TF(P)≤1.01， (1)
TF(ADO
3)＞1.0， (2)
TF (BEO
3)＜1.0, and (3)
TF(BEO
3)＜TF(CFO
3)＜TF(ADO
3)， (4)
Wherein, TF (P) is by composition formula (A, B, C) (D, E, F) O
3The tolerance factor of the piezoelectric oxide of expression, TF (ADO
3) be by composition formula ADO
3The tolerance factor of the mixture of expression, TF (BEO
3) be by composition formula BEO
3The tolerance factor of the mixture of expression, and TF (CFO
3) be by composition formula CFO
3The tolerance factor of the mixture of expression.
4. piezoelectric oxide according to claim 3, the described composition of wherein said perofskite type oxide further satisfy condition (5),
0.98≤TF(CFO
3)≤1.02 (5)。
5. piezoelectric oxide according to claim 3, wherein said composition represented by following composition formula,
(A，B，C)DO
3，
In the formula, each among A, B, C and the D is all represented one or more metallic elements, and A, B and C represent A-bit element, and D represents one or more beta-position elements, and O represents oxygen element, and A-bit plain A, B be different with C, and
The described composition of described perofskite type oxide satisfy condition (1a), (2a), (3a) and (4a),
0.98≤TF(P1)≤1.01， (1a)
TF(ADO
3)＞1.0， (2a)
TF (BDO
3)＜1.0 and (3a)
TF(BDO
3)＜TF(CDO
3)＜TF(ADO
3)， (4a)
In the formula, TF (P1) is the tolerance factor of described perofskite type oxide, TF (BDO
3) be mixture BDO
3Tolerance factor, and TF (CDO
3) be mixture CDO
3Tolerance factor.
6. piezoelectric oxide according to claim 5, the described composition of wherein said perofskite type oxide further satisfy condition (5a),
0.98≤TF(CDO
3)≤1.02 (5a)。
7. piezoelectric oxide according to claim 3, wherein said composition represented by following composition formula,
A(D，E，F)O
3，
In the formula, each among A, D, E and the F is all represented one or more metallic elements, and A represents one or more A-bit elements, and D, E and F represent the beta-position element, and O represents oxygen element, and beta-position element D, E be different with F, and
The described composition of described perofskite type oxide satisfy condition (1b), (2b), (3b) and (4b),
0.98≤TF(P2)≤1.01， (1b)
TF(ADO
3)＞1.0， (2b)
TF (AEO
3)＜1.0 and (3b)
TF(AEO
3)＜TF(AFO
3)＜TF(ADO
3)， (4b)
In the formula, TF (P2) is the tolerance factor of described perofskite type oxide, TF (AEO
3) be mixture AEO
3Tolerance factor, and TF (AFO
3) be mixture AFO
3Tolerance factor.
8. piezoelectric oxide according to claim 7, the described composition of wherein said perofskite type oxide further satisfy condition (5b),
0.98≤TF(AFO
3)≤1.02 (5b)。
9. piezoelectric oxide according to claim 3 contains the first component ADO
3, the second B component EO
3With the 3rd component CFO
3, wherein at the described first component ADO
3, the second B component EO
3With the 3rd component CFO
3Can form separately in the scope of perovskite structure, at the first component ADO
3, the second B component EO
3With the 3rd component CFO
3The molar weight of the A-bit element in each component and the molar weight of beta-position element can depart from 1: 3 with respect to the ratio of the molar weight of Sauerstoffatom separately.
10. piezoelectric oxide according to claim 9, wherein said first component and described each self-forming of second component are corresponding to the crystalline structure of the isomorphous system not.
11. piezoelectric oxide according to claim 9, wherein said first component, described second component and described each self-forming of the 3rd component are corresponding to the crystalline structure of the isomorphous system not.
12. piezoelectric oxide according to claim 10, wherein said first component forms corresponding to the first a kind of crystalline structure in square, oblique side, monocline, three parts and the rhombohedral system, and described second component forms corresponding to the second a kind of crystalline structure in square, oblique side and the rhombohedral system, and described second crystalline structure is different from described first crystalline structure.
13. piezoelectric oxide according to claim 11, wherein said first component forms corresponding to the first a kind of crystalline structure in square, oblique side, monocline, three parts and the rhombohedral system, and described second component forms corresponding to the second a kind of crystalline structure in square, oblique side and the rhombohedral system, and described second crystalline structure is different from described first crystalline structure.
14. piezoelectric oxide according to claim 12, wherein said first crystalline structure is corresponding to described tetragonal spheroidal, and described second crystalline structure is corresponding to described rhombohedral system.
15. piezoelectric oxide according to claim 13, wherein said first crystalline structure is corresponding to described tetragonal spheroidal, and described second crystalline structure is corresponding to described rhombohedral system.
16. piezoelectric oxide according to claim 11, wherein said first component forms corresponding to the first a kind of crystalline structure in square, oblique side, monocline, three parts and the rhombohedral system, described second component forms and is different from described first crystalline structure and corresponding to square, the oblique second a kind of crystalline structure in side and the rhombohedral system, and described the 3rd component form corresponding to cube and false isometric system in the 3rd a kind of crystalline structure.
17. piezoelectric oxide according to claim 16, wherein said first crystalline structure is corresponding to described tetragonal spheroidal, and described second crystalline structure is corresponding to described rhombohedral system.
18. piezoelectric oxide according to claim 3, wherein said composition represented by following composition formula,
Pb(Ti，Zr，M)O
3，
In the formula, M is at least a among metallic element Sn, Nb, Ta, Mo, W, Ir, Os, Pd, Pt, Re, Mn, Co, Ni, V and the Fe.
19. piezoelectric oxide according to claim 3, wherein said composition represented by following composition formula,
(Ba，Ca，Sr)(Ti，Zr，M)O
3，
In the formula, M is at least a among metallic element Sn, Nb, Ta, Mo, W, Ir, Os, Pd, Pt, Re, Mn, Co, Ni, V and the Fe.
20. piezoelectric oxide according to claim 3, wherein said composition represented by following composition formula,
Bi(Al，Fe，M)O
3，
In the formula, M is at least a among metallic element Cr, Mn, Co, Ni, Ga and the Sc.
21. a piezoelectric oxide has;
At morphotropy phase boundary place or near the composition it; And
The mixed-crystal structure that constitutes by at least two kind of first crystalline phase and at least a second crystalline phase, described at least two kind of first crystalline phase is square, oblique at least two kinds in side and the rhombus crystalline phase, described at least a second crystalline phase be cube and false cube crystalline phase at least a.
22. piezoelectric oxide according to claim 21, wherein said mixed-crystal structure by tetragonal phase, rhombus crystalline phase and cube and one of false cube crystalline phase constitute.
23. a piezoelectric oxide has;
At morphotropy phase boundary place or near the composition it; And
Show the structure of the high resolving power x-ray diffraction pattern that comprises following peak: corresponding to first diffraction peak of tetragonal phase, corresponding to second diffraction peak of rhombus crystalline phase, corresponding to the 3rd diffraction peak of the crystalline phase that is different from described tetragonal phase and described rhombus crystalline phase.
24. a ferroelectricity mixture, it contains the described perofskite type oxide of with good grounds claim 3.
25. a ferroelectricity mixture, it contains the described perofskite type oxide of with good grounds claim 21.
26. a ferroelectricity mixture, it contains the described perofskite type oxide of with good grounds claim 23.
27. piezoelectrics, it contains the described perofskite type oxide of with good grounds claim 3.
28. piezoelectrics, it contains the described perofskite type oxide of with good grounds claim 21.
29. piezoelectrics, it contains the described perofskite type oxide of with good grounds claim 23.
30. piezoelectrics according to claim 27, it has the form of piezoelectric film or sintered ceramic body.
31. piezoelectrics according to claim 28, it has the form of piezoelectric film or sintered ceramic body.
32. piezoelectrics according to claim 29, it has the form of piezoelectric film or sintered ceramic body.
33. piezoelectrics according to claim 27, it contains the ferroelectric phase with crystalline orientation.
34. piezoelectrics according to claim 28, it contains the ferroelectric phase with crystalline orientation.
35. piezoelectrics according to claim 29, it contains the ferroelectric phase with crystalline orientation.
36. piezoelectrics according to claim 33, it contains at least a ferroelectric phase, and each in the wherein said at least a ferroelectric phase all has along the spontaneous polarization axle of first direction and along the crystalline orientation that is different from the second direction of described first direction.
37. piezoelectrics according to claim 34, it contains at least a ferroelectric phase, and each in the wherein said at least a ferroelectric phase all has along the spontaneous polarization axle of first direction and along the crystalline orientation that is different from the second direction of described first direction.
38. piezoelectrics according to claim 35, it contains at least a ferroelectric phase, and each in the wherein said at least a ferroelectric phase all has along the spontaneous polarization axle of first direction and along the crystalline orientation that is different from the second direction of described first direction.
39. piezoelectrics according to claim 36, wherein said at least a ferroelectric phase are at least a in the following crystalline phase: approximate tetragonal phase, the crystalline orientation of approximate tetragonal phase, the crystalline orientation of approximate rhombus crystalline phase, the crystalline orientation of approximate rhombus crystalline phase, the crystalline orientation of crystalline orientation along＜111〉direction along＜110〉direction along＜110〉direction along＜100〉direction approximate along＜100〉direction iris mutually and crystalline orientation approximate along＜111〉direction iris phase.
40. according to the described piezoelectrics of claim 37, wherein said at least a ferroelectric phase is at least a in the following crystalline phase: approximate tetragonal phase, the crystalline orientation of approximate tetragonal phase, the crystalline orientation of approximate rhombus crystalline phase, the crystalline orientation of approximate rhombus crystalline phase, the crystalline orientation of crystalline orientation along＜111〉direction along＜110〉direction along＜110〉direction along＜100〉direction approximate along＜100〉direction iris mutually and crystalline orientation approximate along＜111〉direction iris phase.
41. according to the described piezoelectrics of claim 38, wherein said at least a ferroelectric phase is at least a in the following crystalline phase: approximate tetragonal phase, the crystalline orientation of approximate tetragonal phase, the crystalline orientation of approximate rhombus crystalline phase, the crystalline orientation of approximate rhombus crystalline phase, the crystalline orientation of crystalline orientation along＜111〉direction along＜110〉direction along＜110〉direction along＜100〉direction approximate along＜100〉direction iris mutually and crystalline orientation approximate along＜111〉direction iris phase.
42. piezoelectrics according to claim 36, wherein be different from the direction of described first direction when described piezoelectrics apply electric field when the edge, the at least a portion of each is transformed into another kind of ferroelectric phase in the described at least a ferroelectric phase, described another kind of ferroelectric phase corresponding to corresponding to each the different crystallographic system of crystallographic system in the described at least a ferroelectric phase.
43. according to the described piezoelectrics of claim 37, wherein be different from the direction of described first direction when described piezoelectrics apply electric field when the edge, the at least a portion of each is transformed into another kind of ferroelectric phase in the described at least a ferroelectric phase, described another kind of ferroelectric phase corresponding to corresponding to each the different crystallographic system of crystallographic system in the described at least a ferroelectric phase.
44. according to the described piezoelectrics of claim 38, wherein be different from the direction of described first direction when described piezoelectrics apply electric field when the edge, the at least a portion of each is transformed into another kind of ferroelectric phase in the described at least a ferroelectric phase, described another kind of ferroelectric phase corresponding to corresponding to each the different crystallographic system of crystallographic system in the described at least a ferroelectric phase.
45. a piezo-electric device comprises:
Described piezoelectrics according to claim 27; And
Electrode applies electric field by described electrode to described piezoelectrics.
46. a piezo-electric device comprises:
Described piezoelectrics according to claim 28; And
Electrode applies electric field by described electrode to described piezoelectrics.
47. a piezo-electric device comprises:
Piezoelectrics according to claim 29; And
Electrode applies electric field by described electrode to described piezoelectrics.
48. a piezo-electric device comprises:
Piezoelectrics according to claim 36; And
Electrode applies electric field by described electrode to described piezoelectrics.
49. a piezo-electric device comprises:
According to the described piezoelectrics of claim 37; And
Electrode applies electric field by described electrode to described piezoelectrics.
50. a piezo-electric device comprises:
According to the described piezoelectrics of claim 38; And
Electrode applies electric field by described electrode to described piezoelectrics.
51. according to the described piezo-electric device of claim 48, wherein the described electric field that applies to described piezoelectrics by described electrode is along the direction that is different from described first direction.
52. according to the described piezo-electric device of claim 49, wherein the described electric field that applies to described piezoelectrics by described electrode is along the direction that is different from described first direction.
53. according to the described piezo-electric device of claim 50, wherein the described electric field that applies to described piezoelectrics by described electrode is along the direction that is different from described first direction.
54. a liquid discharge device comprises:
Substrate;
Be placed in above-mentioned suprabasil described piezo-electric device according to claim 45; And discharge member, it is with the whole formation of described substrate or separate formation, and comprises:
The deposit liquid the liquid storage chamber and
The liquid discharge outlet, described liquid is discharged described liquid storage chamber by described liquid discharge outlet.
55. a liquid discharge device comprises:
Substrate;
Be placed in above-mentioned suprabasil described piezo-electric device according to claim 46; And discharge member, it is with the whole formation of described substrate or separate formation, and comprises:
The deposit liquid the liquid storage chamber and
The liquid discharge outlet, described liquid is discharged described liquid storage chamber by described liquid discharge outlet.
56. a liquid discharge device comprises:
Substrate;
Be placed in above-mentioned suprabasil described piezo-electric device according to claim 47; And
Discharge member, it is with the whole formation of described substrate or separate formation, and comprises:
The deposit liquid the liquid storage chamber and
The liquid discharge outlet, described liquid is discharged described liquid storage chamber by described liquid discharge outlet.
57. a liquid discharge device comprises:
Substrate;
Be placed in above-mentioned suprabasil described piezo-electric device according to claim 48; And discharge member, it is with the whole formation of described substrate or separate formation, and comprises:
The deposit liquid the liquid storage chamber and
The liquid discharge outlet, described liquid is discharged described liquid storage chamber by described liquid discharge outlet.
58. a liquid discharge device comprises:
Substrate;
Be placed in above-mentioned suprabasil described piezo-electric device according to claim 49; And discharge member, it is with the whole formation of described substrate or separate formation, and comprises:
The deposit liquid the liquid storage chamber and
The liquid discharge outlet, described liquid is discharged described liquid storage chamber by described liquid discharge outlet.
59. a liquid discharge device comprises:
Substrate;
Be placed in above-mentioned suprabasil described piezo-electric device according to claim 50; And discharge member, it is with the whole formation of described substrate or separate formation, and comprises:
The deposit liquid the liquid storage chamber and
The liquid discharge outlet, described liquid is discharged described liquid storage chamber by described liquid discharge outlet.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006250389 | 2006-09-15 | ||
| JP2006-250389 | 2006-09-15 | ||
| JP2006250389 | 2006-09-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101157544A true CN101157544A (en) | 2008-04-09 |
| CN101157544B CN101157544B (en) | 2013-03-06 |
Family
ID=38813296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101542712A Active CN101157544B (en) | 2006-09-15 | 2007-09-17 | Perovskite oxide, process for producing the perovskite oxide, piezoelectric body, piezoelectric device, and liquid discharge device |
Country Status (3)
| Country | Link |
|---|---|
| US (2) | US7918542B2 (en) |
| EP (1) | EP1901361A3 (en) |
| CN (1) | CN101157544B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101621112A (en) * | 2008-06-30 | 2010-01-06 | 日立金属株式会社 | Ceramic sintered compact and piezoelectric element |
| CN101908596A (en) * | 2009-06-08 | 2010-12-08 | 富士胶片株式会社 | Piezoelectric device contains its piezo-activator, liquid discharge device and Blast Furnace Top Gas Recovery Turbine Unit (TRT) |
| CN102031007A (en) * | 2009-09-28 | 2011-04-27 | 富士胶片株式会社 | Polymer composite piezoelectric materials and piezoelectric device using same |
| CN103579491A (en) * | 2012-08-07 | 2014-02-12 | 日立金属株式会社 | Piezoelectric element, piezoelectric device and method of manufacturing piezoelectric element |
| CN104891987A (en) * | 2014-03-07 | 2015-09-09 | 佳能株式会社 | Ceramic powder, piezoelectric ceramic, piezoelectric element, and electronic equipment |
| CN105313466A (en) * | 2014-07-01 | 2016-02-10 | 精工爱普生株式会社 | Piezoelectric element, piezoelectric actuator device, liquid ejecting head, liquid ejecting apparatus, and ultrasonic measuring apparatus |
| CN106103100A (en) * | 2014-03-18 | 2016-11-09 | 精工爱普生株式会社 | Piezoelectric element, piezoelectric actuator device, jet head liquid, liquid injection apparatus and ultrasonic measurement device |
| CN106885120A (en) * | 2017-03-21 | 2017-06-23 | 哈尔滨工业大学 | A kind of micro injection lubricating arrangement of diaphragm seal formula Piezoelectric Driving |
| CN108068458A (en) * | 2016-11-16 | 2018-05-25 | 精工爱普生株式会社 | Piezoelectric element and piezoelectric element application apparatus |
| CN110621638A (en) * | 2017-05-12 | 2019-12-27 | 赛尔科技有限公司 | Ceramic material |
| CN111525024A (en) * | 2020-04-13 | 2020-08-11 | 欧阳俊 | Bismuth ferrite film material, method for integrally preparing bismuth ferrite film on silicon substrate at low temperature and application |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7918542B2 (en) * | 2006-09-15 | 2011-04-05 | Fujifilm Corporation | Perovskite oxide, process for producing the perovskite oxide, piezoelectric body, piezoelectric device, and liquid discharge device |
| JP5546105B2 (en) * | 2007-01-19 | 2014-07-09 | 富士フイルム株式会社 | Perovskite oxide and method for manufacturing the same, piezoelectric film, piezoelectric element, and liquid ejection device |
| JP5127268B2 (en) * | 2007-03-02 | 2013-01-23 | キヤノン株式会社 | Piezoelectric body, piezoelectric element, liquid discharge head and liquid discharge apparatus using the piezoelectric element |
| JP2008311634A (en) * | 2007-05-14 | 2008-12-25 | Fujifilm Corp | Piezoelectric element, method for driving the same, piezoelectric device, and liquid discharge device |
| JP4931148B2 (en) * | 2007-10-02 | 2012-05-16 | 富士フイルム株式会社 | Perovskite oxide stack, piezoelectric element, and liquid ejection device |
| JP5426861B2 (en) * | 2007-10-24 | 2014-02-26 | 富士フイルム株式会社 | Ferroelectric oxide and manufacturing method thereof, piezoelectric body, piezoelectric element |
| JP2009214313A (en) * | 2008-03-07 | 2009-09-24 | Fujifilm Corp | Liquid discharge device |
| JP5507097B2 (en) * | 2008-03-12 | 2014-05-28 | 富士フイルム株式会社 | Perovskite oxide and method for producing the same, piezoelectric body, piezoelectric element, and liquid ejection device |
| US8871111B2 (en) * | 2008-03-18 | 2014-10-28 | Ngk Insulators, Ltd. | Piezoelectric/electrostrictive ceramic composition |
| JP5313792B2 (en) * | 2008-07-17 | 2013-10-09 | 富士フイルム株式会社 | Perovskite oxide, oxide composition, oxide body, piezoelectric element, and liquid ejection device |
| JP2010089470A (en) * | 2008-10-10 | 2010-04-22 | Seiko Epson Corp | Liquid injection head, liquid injection device, and actuator device |
| US8164234B2 (en) | 2009-02-26 | 2012-04-24 | Fujifilm Corporation | Sputtered piezoelectric material |
| US8400047B2 (en) * | 2009-03-12 | 2013-03-19 | Canon Kabushiki Kaisha | Piezoelectric material, piezoelectric device, and method of producing the piezoelectric device |
| JP5681398B2 (en) * | 2009-07-09 | 2015-03-04 | 富士フイルム株式会社 | Perovskite oxide, ferroelectric composition, piezoelectric body, piezoelectric element, and liquid ejection device |
| FR2950197A1 (en) * | 2009-09-15 | 2011-03-18 | Commissariat Energie Atomique | OPTIMIZED OPTIONAL PIEZOELECTRIC MEMBRANE AND PROCESS FOR MANUFACTURING THE MEMBRANE |
| JP4979784B2 (en) * | 2010-02-26 | 2012-07-18 | キヤノン株式会社 | Printing device |
| JP2011181866A (en) * | 2010-03-04 | 2011-09-15 | Fujifilm Corp | Laminated structure and piezoelectric device using the same |
| JP2012106902A (en) * | 2010-10-25 | 2012-06-07 | Fujifilm Corp | Perovskite-type oxide film, ferroelectric film using the same, ferroelectric device, and method for manufacturing perovskite-type oxide film |
| JP6390170B2 (en) * | 2014-05-28 | 2018-09-19 | 株式会社リコー | ELECTRO-MECHANICAL CONVERSION ELEMENT, ELECTRO-MECHANICAL CONVERSION ELEMENT MANUFACTURING METHOD, DROPLET DISCHARGE HEAD, DROPLET DISCHARGE DEVICE |
| US10749056B2 (en) | 2016-02-11 | 2020-08-18 | Drexel University | Method for making ferroelectric material thin films |
| TWI717498B (en) * | 2016-06-21 | 2021-02-01 | 日商前進材料科技股份有限公司 | Membrane structure and manufacturing method thereof |
| JP2018085403A (en) | 2016-11-22 | 2018-05-31 | セイコーエプソン株式会社 | Method for evaluating piezoelectric film, piezoelectric element, liquid injection head, and liquid injection apparatus |
| WO2018234069A1 (en) * | 2017-06-22 | 2018-12-27 | OCE Holding B.V. | A method of manufacturing an inkjet print head and an inkjet print head with induced crystal phase change actuation |
| JP6891734B2 (en) | 2017-08-29 | 2021-06-18 | セイコーエプソン株式会社 | Piezoelectric element and liquid discharge head |
Family Cites Families (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US229384A (en) * | 1880-06-29 | Reversible filter | ||
| US372121A (en) * | 1887-10-25 | Cable-grip for railways | ||
| US6620A (en) * | 1849-07-31 | Improvement in plows | ||
| US139911A (en) * | 1873-06-17 | Improvement in machines for grinding hay | ||
| US1193878A (en) * | 1916-08-08 | filippo | ||
| US144411A (en) * | 1873-11-11 | Improvement in tenoning-machines | ||
| US31622A (en) * | 1861-03-05 | Improved method of jointing telegraphic conductors | ||
| US185935A (en) * | 1877-01-02 | Improvement in cradle-snath bands | ||
| US3144411A (en) | 1961-11-13 | 1964-08-11 | Clevite Corp | Barium-continaining lead titanate ferroelectric compositions and articles |
| US3372121A (en) | 1965-03-15 | 1968-03-05 | Ngk Spark Plug Co | Piezoelectric and electrostrictive ceramic articles of lead zirconate titanate containing manganese and tungsten oxides |
| US3484377A (en) * | 1966-12-08 | 1969-12-16 | Nippon Electric Co | Piezoelectric ceramic material |
| JPS59182273A (en) | 1983-03-31 | 1984-10-17 | 太陽誘電株式会社 | Dielectric ceramic composition |
| US5453262A (en) * | 1988-12-09 | 1995-09-26 | Battelle Memorial Institute | Continuous process for production of ceramic powders with controlled morphology |
| EP0734031B1 (en) * | 1995-03-24 | 2004-06-09 | TDK Corporation | Multilayer varistor |
| JPH09241072A (en) | 1996-03-05 | 1997-09-16 | Ngk Insulators Ltd | Electric field induction strain material |
| US20020036282A1 (en) | 1998-10-19 | 2002-03-28 | Yet-Ming Chiang | Electromechanical actuators |
| JP3568107B2 (en) | 1999-05-17 | 2004-09-22 | セイコーエプソン株式会社 | Actuator, inkjet recording head and inkjet printer |
| US6793843B2 (en) | 2000-11-21 | 2004-09-21 | Tdk Corporation | Piezoelectric ceramic |
| US6685849B2 (en) | 2001-05-14 | 2004-02-03 | The Penn State Research Foundation | Perovskite materials for high temperature and high performance actuators and transducers |
| DE10225704A1 (en) | 2001-06-11 | 2003-01-23 | Denso Corp | Piezoelectric actuator and method for driving it |
| DE10135531A1 (en) * | 2001-07-20 | 2003-03-27 | Reishauer Ag | Method and device for detecting a state of wear of tools used in gear manufacturing |
| DE10229086A1 (en) | 2001-09-29 | 2003-04-17 | Ceramtec Ag | Piezoelectric ceramic materials based on lead zirconate titanate (PZT) with the crystal structure of the perovskite |
| JP2004059369A (en) | 2002-07-29 | 2004-02-26 | Brother Ind Ltd | Piezoelectric porcelain composition and piezoelectric actuator for inkjet head using the same |
| CN1329927C (en) * | 2002-10-24 | 2007-08-01 | 精工爱普生株式会社 | Ferroelectric film, ferroelectric capacitor, ferroelectric memory, piezoelectric device, semiconductor device, method for manufacturing ferroelectric film, and method for manufacturing ferroelectric c |
| JP2004311924A (en) | 2003-03-26 | 2004-11-04 | Seiko Epson Corp | Ferroelectric capacitor and its manufacturing method, ferroelectric memory and piezo-electric element |
| JP4521751B2 (en) * | 2003-03-26 | 2010-08-11 | 国立大学法人東京工業大学 | Lead zirconate titanate-based film, dielectric element, and method for manufacturing dielectric film |
| JP3863124B2 (en) * | 2003-05-08 | 2006-12-27 | 株式会社東芝 | Semiconductor memory device and test method thereof |
| US7312558B2 (en) | 2004-04-02 | 2007-12-25 | Matsushita Electric Industrial Co., Ltd. | Piezoelectric element, ink jet head, angular velocity sensor, and ink jet recording apparatus |
| JP2005333108A (en) | 2004-04-02 | 2005-12-02 | Matsushita Electric Ind Co Ltd | Piezoelectric element, ink jet head, angular rate sensor, and ink jet type recording device |
| JP2006036578A (en) | 2004-07-27 | 2006-02-09 | Matsushita Electric Ind Co Ltd | Method of manufacturing piezoelectric material and piezoelectric material using the same |
| JP4375560B2 (en) | 2004-12-07 | 2009-12-02 | セイコーエプソン株式会社 | Method for manufacturing transistor-type ferroelectric memory |
| ATE498358T1 (en) | 2005-06-29 | 2011-03-15 | Compumedics Ltd | SENSOR ARRANGEMENT WITH CONDUCTIVE BRIDGE |
| JP4953351B2 (en) | 2005-08-23 | 2012-06-13 | キヤノン株式会社 | Perovskite oxide, piezoelectric element using the same, liquid discharge head, and liquid discharge apparatus |
| US8142678B2 (en) | 2005-08-23 | 2012-03-27 | Canon Kabushiki Kaisha | Perovskite type oxide material, piezoelectric element, liquid discharge head and liquid discharge apparatus using the same, and method of producing perovskite type oxide material |
| JP4237208B2 (en) | 2005-09-26 | 2009-03-11 | 富士フイルム株式会社 | Piezoelectric element and driving method thereof, piezoelectric device, and liquid ejection device |
| US7918542B2 (en) * | 2006-09-15 | 2011-04-05 | Fujifilm Corporation | Perovskite oxide, process for producing the perovskite oxide, piezoelectric body, piezoelectric device, and liquid discharge device |
| JP5127268B2 (en) * | 2007-03-02 | 2013-01-23 | キヤノン株式会社 | Piezoelectric body, piezoelectric element, liquid discharge head and liquid discharge apparatus using the piezoelectric element |
-
2007
- 2007-09-13 US US11/898,621 patent/US7918542B2/en active Active
- 2007-09-14 EP EP07018069A patent/EP1901361A3/en not_active Withdrawn
- 2007-09-17 CN CN2007101542712A patent/CN101157544B/en active Active
-
2011
- 2011-03-04 US US13/040,592 patent/US8434856B2/en active Active
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101621112A (en) * | 2008-06-30 | 2010-01-06 | 日立金属株式会社 | Ceramic sintered compact and piezoelectric element |
| CN101621112B (en) * | 2008-06-30 | 2013-11-06 | 日立金属株式会社 | Ceramic sintered compact and piezoelectric element |
| CN101908596A (en) * | 2009-06-08 | 2010-12-08 | 富士胶片株式会社 | Piezoelectric device contains its piezo-activator, liquid discharge device and Blast Furnace Top Gas Recovery Turbine Unit (TRT) |
| CN101908596B (en) * | 2009-06-08 | 2014-09-17 | 富士胶片株式会社 | Piezoelectric device, piezoelectric actuator having the same, liquid discharge apparatus, and power generating apparatus |
| CN102031007A (en) * | 2009-09-28 | 2011-04-27 | 富士胶片株式会社 | Polymer composite piezoelectric materials and piezoelectric device using same |
| CN102031007B (en) * | 2009-09-28 | 2015-04-08 | 富士胶片株式会社 | Polymer composite piezoelectric materials and piezoelectric device using same |
| CN103579491A (en) * | 2012-08-07 | 2014-02-12 | 日立金属株式会社 | Piezoelectric element, piezoelectric device and method of manufacturing piezoelectric element |
| CN103579491B (en) * | 2012-08-07 | 2018-01-30 | 住友化学株式会社 | Piezoelectric element, piezoelectrics equipment and its manufacture method |
| US9680085B2 (en) | 2014-03-07 | 2017-06-13 | Canon Kabushiki Kaisha | Ceramic powder, piezoelectric ceramic, piezoelectric element, and electronic equipment |
| CN104891987A (en) * | 2014-03-07 | 2015-09-09 | 佳能株式会社 | Ceramic powder, piezoelectric ceramic, piezoelectric element, and electronic equipment |
| CN106103100A (en) * | 2014-03-18 | 2016-11-09 | 精工爱普生株式会社 | Piezoelectric element, piezoelectric actuator device, jet head liquid, liquid injection apparatus and ultrasonic measurement device |
| CN106103100B (en) * | 2014-03-18 | 2017-10-24 | 精工爱普生株式会社 | Piezoelectric element, piezoelectric actuator device, jet head liquid, liquid injection apparatus and ultrasonic measurement device |
| CN105313466A (en) * | 2014-07-01 | 2016-02-10 | 精工爱普生株式会社 | Piezoelectric element, piezoelectric actuator device, liquid ejecting head, liquid ejecting apparatus, and ultrasonic measuring apparatus |
| CN105313466B (en) * | 2014-07-01 | 2019-05-28 | 精工爱普生株式会社 | Piezoelectric element, piezoelectric actuator device, liquid ejecting head and the device using it |
| CN108068458A (en) * | 2016-11-16 | 2018-05-25 | 精工爱普生株式会社 | Piezoelectric element and piezoelectric element application apparatus |
| CN106885120A (en) * | 2017-03-21 | 2017-06-23 | 哈尔滨工业大学 | A kind of micro injection lubricating arrangement of diaphragm seal formula Piezoelectric Driving |
| CN106885120B (en) * | 2017-03-21 | 2018-09-07 | 哈尔滨工业大学 | A kind of micro injection lubricating arrangement of diaphragm seal formula Piezoelectric Driving |
| CN110621638A (en) * | 2017-05-12 | 2019-12-27 | 赛尔科技有限公司 | Ceramic material |
| US11873253B2 (en) | 2017-05-12 | 2024-01-16 | Xaar Technology Limited | Ceramic |
| CN111525024A (en) * | 2020-04-13 | 2020-08-11 | 欧阳俊 | Bismuth ferrite film material, method for integrally preparing bismuth ferrite film on silicon substrate at low temperature and application |
| CN111525024B (en) * | 2020-04-13 | 2022-04-05 | 欧阳俊 | Bismuth ferrite film material, method for integrally preparing bismuth ferrite film on silicon substrate at low temperature and application |
Also Published As
| Publication number | Publication date |
|---|---|
| US20110216132A1 (en) | 2011-09-08 |
| EP1901361A2 (en) | 2008-03-19 |
| US7918542B2 (en) | 2011-04-05 |
| US20080074471A1 (en) | 2008-03-27 |
| EP1901361A3 (en) | 2009-08-05 |
| US8434856B2 (en) | 2013-05-07 |
| CN101157544B (en) | 2013-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101157544B (en) | Perovskite oxide, process for producing the perovskite oxide, piezoelectric body, piezoelectric device, and liquid discharge device | |
| US8177995B2 (en) | Perovskite oxide, process for producing the perovskite oxide, and piezoelectric device | |
| US7997692B2 (en) | Perovskite oxide, process for producing the same, piezoelectric film, and piezoelectric device | |
| US8598769B2 (en) | Perovskite oxide material, ferroelectric compound, piezoelectric body, piezoelectric device, and liquid discharge device | |
| US20080302658A1 (en) | Oxide body, piezoelectric device, and liquid discharge device | |
| US8405285B2 (en) | Piezoelectric device, piezoelectric actuator having the same, liquid discharge apparatus, and power generating apparatus | |
| US8137461B2 (en) | Piezoelectric substrate, piezoelectric element, liquid discharge head and liquid discharge apparatus | |
| EP2145975A2 (en) | Perovskite oxide, oxide composition, oxide body, piezoelectric device, and liquid discharge apparatus | |
| US20080297005A1 (en) | Piezoelectric device, process for driving the piezoelectric device, and piezoelectric actuator | |
| JP5290551B2 (en) | Perovskite oxide and method for producing the same, piezoelectric body, piezoelectric element, and liquid ejection device | |
| JP5616126B2 (en) | Perovskite oxide, oxide composition, oxide body, piezoelectric element, and liquid ejection device | |
| US8151727B2 (en) | Perovskite-oxide film, piezoelectric device, and liquid discharge device | |
| US8215753B2 (en) | Piezoelectric material, method for producing piezoelectric material, piezoelectric device and liquid discharge device | |
| JP2010067756A (en) | Piezoelectric film, piezoelectric element, and liquid discharge device | |
| Akiyama et al. | Development of lead zirconate titanate family thick films on various substrates | |
| US20090108706A1 (en) | Ferroelectric oxide, process for producing the same, piezoelectric body, and piezoelectric device | |
| JP5110703B2 (en) | Perovskite oxide film, ferroelectric, piezoelectric element, liquid ejection device | |
| JP2008192867A (en) | Perovskite oxide and manufacturing method thereof, piezoelectric film, piezoelectric element, and liquid discharge device | |
| Wasa | Thin film technologies for manufacturing piezoelectric materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |